CN1173227A - Block Copolymer Based Polymers - Google Patents
- ️Wed Feb 11 1998
本发明涉及新的基于链段共聚物例如嵌段共聚物的聚合物，它特别适合制备模制体，另外涉及含有这类聚合物的模制体，还涉及聚合物在制备模制体中的应用和制备聚合物和模制体的方法。优选的模制体是眼科的镜片，特别是隐形眼镜(Kontaktlinsen)。此外这种聚合物与已知聚合物相比特色为其含有嵌入在嵌段分隔位置上的光引发剂的基团。嵌段的连接在光化学的反应中进行，它可大大地控制末端或悬垂端成长的聚合物嵌段的链长。对链段共聚物理解为本发明的嵌段共聚物，接枝共聚物，特别是梳型共聚物或星型共聚物。The present invention relates to novel polymers based on segmental copolymers, such as block copolymers, which are particularly suitable for the production of molded bodies, furthermore to molded bodies containing such polymers, and also to the use of polymers in the production of molded bodies Methods of using and preparing polymers and molded bodies. Preferred molded bodies are ophthalmic lenses, especially contact lenses. Furthermore, this polymer is distinguished from known polymers in that it contains groups of photoinitiators embedded at block-separating positions. The linking of the blocks is carried out in a photochemical reaction, which can greatly control the chain length of the growing polymer block at the terminal or pendant end. Segmented copolymers are understood to be block copolymers, graft copolymers, in particular comb copolymers or star copolymers according to the invention.
本发明的链段共聚物具有通式I，
本发明的式I链段共聚物可由下述组分构成：The segmented copolymer of formula I of the present invention can be made of following components:
式A大基体：Formula A large matrix:
Macro-(RxH)m (A)式中Macro，Rx和m如上述所定义但Rx不是键，第二为式B光引发剂。Macro-(R x H) m (A) In the formula, Macro, R x and m are as defined above but R x is not a bond, and the second is the photoinitiator of formula B.
OCN-PI*-Raa (B)式中PI*如上述定义并Raa为光引发剂部分，它在光引发剂分裂时形成弱反应的自由基，第三为乙烯基单体，它作为组成部分“A”被嵌进链段共聚物中，其中A如上述定义。In the OCN-PI * -R aa (B) formula, PI * is as defined above and R aa is the photoinitiator part, which forms a weakly reactive free radical when the photoinitiator splits, and the third is a vinyl monomer, which acts as The moiety "A" is embedded in the segmented copolymer, wherein A is as defined above.
本发明的适宜的式A大基体具有m个基-RxH，其中它涉及羟基(也涉及是羧基-COOH的组成部分的基团)，氨基或低级烷基氨基(也涉及是酰胺基-CONRN的组成部分的基团)或巯基。这些基是与式B光引发剂的异氰酸酯基共反应的。式A大基体适宜与m摩尔当量式B光引发剂反应成式(C)大基体
这样形成的式C大基体含有经一桥-O-CO-NH-，-CO-NH-，-NRN-CO-NH-，-CO-NRN-CO-NH-或-S-CO-NH-结合的m个式B光引发剂，它在另外的步骤中与p摩尔当量乙烯基单体反应，后者作为组成部分“A”嵌入到式I共聚物中。链终止例如是通过式B光引发剂的弱反应的自由基Raa或通过其他的适宜的链终止剂实现的，链终止剂在反应条件下处于反应混合物中，例如H-自由基或OH-自由基或由溶剂形成的自由基。变量Ra是优选式B光引发剂的组成部分Raa。The large matrix of formula C thus formed contains a bridge -O-CO-NH-, -CO-NH-, -NR N -CO-NH-, -CO-NR N -CO-NH- or -S-CO- NH-bonded m photoinitiators of formula B which are reacted in a further step with p molar equivalents of vinyl monomers which are incorporated as constituent "A" into the copolymer of formula I. Chain termination is achieved, for example, by the weakly reactive free radical R aa of the photoinitiator of formula B or by other suitable chain terminators, which are present in the reaction mixture under the reaction conditions, such as H-radicals or OH- Free radicals or free radicals formed from solvents. The variable R a is the preferred formula B photoinitiator moiety R aa .
Rx“键”的含义只对下述情况是重要的：在大基体中OH基是COOH-基的组成部分。COOH-基与异氰酸酯在分裂出CO2情况和在形成键“-CO-NH-”情况下进行反应。只在这种情况下Rx在反应产物中为一键，但不是在含“Rx-H”基的原料中。The meaning of the "bond" of Rx is only important if the OH group is a constituent of the COOH group in the macromatrix. COOH-groups react with isocyanates with splitting of CO 2 and with the formation of bonds "-CO-NH-". Only in this case is R x a bond in the reaction product, but not in the starting material containing the "R x -H" group.
角标p优选为5至200的一个数，特别是10至100的一个数。The subscript p is preferably a number from 5 to 200, especially a number from 10 to 100.
角标m优选为2至15的一个数。最优选角标m为2至5的一个数。The subscript m is preferably a number from 2 to 15. Most preferably subscript m is a number from 2 to 5.
这些基(其中，视角标m的含义而定，1至100是连结在式A的大基体上)或是末端的或悬垂的或是末端的和悬垂的。These groups (where 1 to 100 are attached to the macromatrix of formula A, depending on the meaning of the index m) are either terminal or pendant or both terminal and pendant.
在一特别优选的实施方案中式A大基体有二个末端的基RxH，一种由此形成的本发明式I链段共聚物或式I嵌段共聚物同样是优选的并在此发明中被称为三嵌段共聚物：中央的嵌段由大基体构成，在其上结合了二个光引发剂，两个末端的嵌段主要由二价基A构成。In a particularly preferred embodiment the macromatrix of the formula A has two terminal radicals R x H, a segmented copolymer of the formula I or a block copolymer of the formula I thus formed is also preferred and invented here It is called a three-block copolymer: the central block is composed of a large matrix, on which two photoinitiators are combined, and the two terminal blocks are mainly composed of divalent groups A.
在另一优选实施方案中式A大基体只具有悬垂的基RxH。一种由此形成的本发明式I链段共聚物或式I接枝共聚物同样是优选的并在此发明中被称为梳型共聚物：梳的背或横挡由大基体构成，多个光引发剂悬垂结合其上，梳的尖齿或牙主要由二价基A构成，它是经光引发剂的基结合的。In another preferred embodiment the macromatrix of the formula A has only pendant radicals R x H. A segmented copolymer of the formula I or a graft copolymer of the formula I thus formed according to the invention is likewise preferred and is referred to in this invention as a comb copolymer: the back or bar of the comb consists of a large matrix, more A photoinitiator pendant is bound to it, and the tines or teeth of the comb are mainly composed of divalent radicals A, which are bound by the radicals of the photoinitiator.
在另一优选实施方案中式A环状的大基体具有悬垂的基RxH，一种由此形成的本发明式I链段共聚物或式I接枝共聚物同样是优选的并在此发明中被称为星型聚合物；星的中点由大基体构成，其上悬垂地结合了多个光引发剂，星的辐射主要是通过二价的基A构成，它是经光引发剂的基结合的。In another preferred embodiment the cyclic macromatrix of the formula A has pendant radicals R x H, a segmented copolymer of the formula I or a graft copolymer of the formula I thus formed is likewise preferred and invented here It is called a star polymer; the midpoint of the star is composed of a large matrix, on which multiple photoinitiators are pendantly combined. base bonded.
有意义的是，所有式I的本发明的共聚物和由此得到的交联聚合物出乎预料的在其性能上都与传统的共聚物和聚合物有区别。这种情况一方面是因为乙烯基单体的链长(参见式I中的-(A)P-)按照本发明可以尽量的控制。另外式I共聚物出乎意料地没有或至少基本没有各使用的乙烯基单体的均聚物，如它们与其他的在文献中所描叙的自由的大引发剂经常构成的。这些有利的性能在制备本发明的聚合物的过程中可转用到其上。It is interesting that all inventive copolymers of the formula I and the crosslinked polymers obtained therefrom differ unexpectedly in their properties from conventional copolymers and polymers. This situation is due to the fact that the chain length of the vinyl monomer (see -(A) P - in formula I) can be controlled as much as possible according to the present invention. Furthermore, the copolymers of the formula I are surprisingly free, or at least essentially free, of homopolymers of the respective vinyl monomers used, as they are often formed with other free macroinitiators described in the literature. These advantageous properties can be transferred to the polymers of the invention during their preparation.
这样本发明的链段共聚物可针对地反应或进一步加工成后面的产物。特别应强调的情况是，未交联的式I共聚物可以简单的方法嵌入交联聚合物中，例如通过使式C化合物与当时的乙烯基单体在交联剂存在下进行反应。对这类交联的补充，或另一方面，本发明的式I共聚物可得以改性，若共聚物在按照式I的-(A)p-部分中具有反应基的话。The segmented copolymers according to the invention can thus be reacted in a targeted manner or further processed to give subsequent products. It should be emphasized in particular that the non-crosslinked copolymers of the formula I can be incorporated into crosslinked polymers in a simple manner, for example by reacting the compounds of the formula C with the vinyl monomers present in the presence of crosslinkers. Complementary to such crosslinking, or alternatively, the copolymers of the formula I according to the invention can be modified if the copolymers have reactive groups in the -(A) p -moiety according to the formula I.
因此本发明的交联聚合物涉及有聚合能力的混合物的聚合产物，这种混合物含有下面的组分：The crosslinked polymers of the present invention therefore relate to the polymerisation product of a polymerisable mixture comprising the following components:
a)式C大基体
b)可共聚合的乙烯基单体和b) copolymerizable vinyl monomers and
c)交联剂c) Cross-linking agent
另外本发明的聚合物涉及这种聚合物产物，它通过下述方法得到：使前面提到的组分a)，b)和c)以本身已知的方法，和特别是如在后面详细描述的，互相反应。In addition the polymer of the present invention relates to this polymer product, and it obtains by following method: make above-mentioned component a), b) and c) with the method known per se, and in particular as described in detail below , react to each other.
投入使用的式C大基体优选的数量为10至90％重量，特别是20至80％重量，投入使用的可共聚合的乙烯基单体同样优选的数量为10至90％重量，特别是20至80％重量，其中这种百分数数值是以相互有关的组分量为基的。投入使用的交联剂优选的数量为直至25％重量，特别是数量直至12.5％重量，以组分a)和b)总和为基。这种优选的％重量数值也适用于交联剂组分，这种交联剂组分是通过共聚合的乙烯基单体的后来的改性得到的。The macromatrix of formula C put into use is preferably in an amount of 10 to 90% by weight, especially 20 to 80% by weight, and the copolymerizable vinyl monomer put into use is also preferably in an amount of 10 to 90% by weight, especially 20% by weight. to 80% by weight, where such percentage values are based on the amounts of the components in relation to each other. The crosslinkers are preferably used in amounts of up to 25% by weight, in particular in amounts of up to 12.5% by weight, based on the sum of components a) and b). This preferred weight % figure also applies to the crosslinker component obtained by subsequent modification of the copolymerized vinyl monomers.
交联剂，如前面作为组分c)提到的，可涉及典型的可共聚的低聚乙烯基的交联剂，如在现有技术已知的，在制备本发明聚合物的聚合开始前，将它加到可聚合的混合物中。The cross-linking agent, as mentioned above as component c), may involve typical copolymerizable oligoethylene-based cross-linking agents, as known in the prior art, before the start of the polymerization to prepare the polymer of the invention , adding it to the polymerizable mixture.
另一方面交联剂可涉及低官能的化合物，这种化合物与在-(A)p-部分中含有的反应基是共反应的。对在-(A)p-部分的反应基例如理解为OH-基，这里低官能化合物的共反应的基例如是异氰酸酯基，羧基，也作为酐，环氧基。因此适宜的低官能的化合物例如是二异氰酸酯，三异氰酸酯，二酐，二羧酸或二环氧化物。在-(A)p-部分中的另一种反应基例如是COOH-基，这里共反应基例如是氨基或羟基。适宜的低官能的化合物因此在这种情况例如是二胺，二醇或氨基醇，另外的例子是专业技术人员已知的。Crosslinkers on the other hand may involve low-functional compounds which are co-reactive with the reactive groups contained in the -(A) p - moieties. Reactive groups in the moiety -(A) p- are understood, for example, to be OH-groups, co-reactive groups of low-functional compounds here being, for example, isocyanate groups, carboxyl groups, also as anhydrides, epoxy groups. Suitable low-functional compounds are thus, for example, diisocyanates, triisocyanates, dianhydrides, dicarboxylic acids or diepoxides. Another reactive group in the moiety -(A) p- is, for example, a COOH- group, where co-reactive groups are, for example, amino or hydroxyl groups. Suitable low-functional compounds are thus in this case, for example, diamines, diols or aminoalcohols, further examples being known to the skilled person.
交联的另一可能性是进一步改性在-(A)P-部分中的反应基，使它转化成可交联的基。下面将给出这类改性的例子。Another possibility for crosslinking is to further modify the reactive group in the -(A) P- moiety, converting it into a crosslinkable group. Examples of such modifications will be given below.
这类的反应基例如可涉及羟基，它来自乙烯基单体如(甲基)丙烯酸羟基低级烷基酯，例如甲基丙烯酸2-羟基乙基酯或甲基丙烯酸3-羟基丙基酯；或来自聚乙烯醇，它们以后与乙烯基异氰酸酯，例如甲基丙烯酸2-异氰酸根合乙基酯，进行反应。乙烯基异氰酸酯的C-C-双键(它以这样所描述的方式被嵌入)可交联成本发明的聚合物和/或与另外的乙烯基单体或二乙烯基单体共聚合。Such reactive groups may, for example, involve hydroxyl groups derived from vinyl monomers such as hydroxy lower alkyl (meth)acrylates, for example 2-hydroxyethyl methacrylate or 3-hydroxypropyl methacrylate; or From polyvinyl alcohols, which are subsequently reacted with vinyl isocyanates, such as 2-isocyanatoethyl methacrylate. The C-C-double bonds of the vinyl isocyanates, which are intercalated in the manner thus described, can be crosslinked to the polymers of the invention and/or copolymerized with further vinyl or divinyl monomers.
这类的反应基例如可涉及异氰酸酯基团，羧基或环氧基，它们是来自乙烯基异氰酸酯，乙烯基羧酸或乙烯基环氧化合物，例如来自甲基丙烯酸2-异氰酸根合乙基酯，(甲基)丙烯酸或(甲基)丙烯酸缩水甘油酯，它们随后与(甲基)丙烯酸羟基低级烷基酯，例如甲基丙烯酸2-羟乙基酯或甲基丙烯酸3-羟丙基酯进行反应。(甲基)丙烯酸羟基低级烷基酯的C-C双键(它以这样描述的方式嵌入)可交联成本发明的聚合物和/或与另外的乙烯基单体或二乙烯基单体共聚合。Such reactive groups may, for example, be isocyanate groups, carboxyl groups or epoxy groups derived from vinyl isocyanate, vinyl carboxylic acid or vinyl epoxy compounds, such as from 2-isocyanatoethyl methacrylate , (meth)acrylic acid or glycidyl (meth)acrylate, which are subsequently combined with hydroxy lower alkyl (meth)acrylates such as 2-hydroxyethyl methacrylate or 3-hydroxypropyl methacrylate react. The C-C double bonds of the hydroxy lower alkyl (meth)acrylates, which are embedded in the manner thus described, can be crosslinked into the polymers of the invention and/or copolymerized with additional vinyl or divinyl monomers.
前面的和后面的“(甲基)丙烯酸酯”缩写表达为“甲基丙烯酸酯或丙烯酸酯”。The preceding and following "(meth)acrylate" abbreviations are expressed as "methacrylate or acrylate".
所有前面提到的性能使本发明的聚合物适于作为不同类别的模制体充满各使用领域，如作为生物医学的物质，例如植入物，眼科的镜片，特别是角膜，眼球晶片体或，最优选，隐形眼镜，或作为医学的仪器，器具，隔膜，药输送系统，或作为在无机的和有机的物质上的涂层。此外未交联的式I链段共聚物不仅适于作为本发明聚合物的原料，而且也突出的适于作为涂层物质。与亲水组分“A”生成两亲的嵌段聚合物，梳型聚合物或星型聚合物，它们具有表面活化的性能并适合例如作乳化剂。All of the aforementioned properties make the polymers according to the invention suitable as molded bodies of different classes to fill various fields of use, such as biomedical substances, such as implants, ophthalmic lenses, especially the cornea, ophthalmic lens bodies or , most preferably, contact lenses, or as medical instruments, implements, diaphragms, drug delivery systems, or as coatings on inorganic and organic substances. Furthermore, uncrosslinked segmental copolymers of the formula I are suitable not only as starting materials for the polymers of the invention, but also eminently also as coating substances. With the hydrophilic component "A" amphiphilic block polymers, comb polymers or star polymers are formed which have surface-active properties and are suitable, for example, as emulsifiers.
因此本发明涉及未交联形式的式I共聚物，特别优选作为三嵌段共聚物，作为梳型聚合物或作为星型聚合物。另外本发明涉及如前面定义的交联的聚合物，含有提到的组分作为主要的或唯一的组分。另外本发明涉及以式I共聚物为基础的接枝共聚物，它是通过下述方法改性的，在-(A)p-部分含有的或在那里经反应基引入的乙烯基上接枝了一个乙烯基单体或多个乙烯基单体。另外本发明涉及由提到的共聚物，聚合物或接枝共聚物制成的模制体，特别是隐形眼镜。另外本发明涉及在应用所述原料和后面的操作条件下制备提到的共聚物，聚合物或接枝共聚物的方法。另外本发明涉及提到的共聚物，聚合物或接枝共聚物形成模制体，特别是隐形眼镜的制备，以及提到的共聚物，聚合物或接枝共聚物在制备模制体，特别是隐形眼镜中的应用。The present invention therefore relates to copolymers of the formula I in uncrosslinked form, particularly preferably as triblock copolymers, as comb polymers or as star polymers. Furthermore the invention relates to crosslinked polymers as defined above, containing the components mentioned as main or sole components. In addition, the invention relates to graft copolymers based on copolymers of the formula I, which are modified by grafting on the vinyl groups contained in the -(A) p -part or introduced there via reactive groups One vinyl monomer or multiple vinyl monomers. Furthermore the invention relates to molded bodies, in particular contact lenses, made of the copolymers, polymers or graft copolymers mentioned. Furthermore the invention relates to a process for the preparation of the mentioned copolymers, polymers or graft copolymers using said starting materials and subsequent operating conditions. Furthermore the invention relates to the preparation of the mentioned copolymers, polymers or graft copolymers for the formation of molded bodies, in particular contact lenses, and the use of the mentioned copolymers, polymers or graft copolymers for the preparation of molded bodies, in particular It is an application in contact lenses.
式A大基体优选涉及低聚物或聚合物，其平均分子量为300至10000道尔顿，并它们优选含有至少3，优选3至50和特别优选5至20个结构以单元。在低聚物和聚合物之间的过渡已知是连续的和不能准确划开的。聚合物可含有50至10000，优选50至5000结构单元并具有平均分子量为10000至2000000，优选10000至500000。低聚物和聚合物也可含有直至95mol-％，优选5至90mol-％共聚用单体的结构单元而无H-活化基(此术语在这里与“RxH-基”含义相同，后者定义如前，附加说明，Rx在这种情况与键不同)，以聚合物为基。The macromatrixes of the formula A are preferably oligomers or polymers whose average molecular weight is from 300 to 10,000 Daltons and which preferably contain at least 3, preferably 3 to 50 and particularly preferably 5 to 20 structural units. The transition between oligomers and polymers is known to be continuous and cannot be demarcated exactly. The polymers may contain 50 to 10,000, preferably 50 to 5,000 structural units and have an average molecular weight of 10,000 to 2,000,000, preferably 10,000 to 500,000. Oligomers and polymers may also contain up to 95 mol-%, preferably 5 to 90 mol-%, of comonomer structural units without H-activating groups (this term is here synonymous with "R x H-groups", hereinafter or are defined as before, with the addition that Rx is in this case different from a bond), based on a polymer.
具有H-活化基的低聚物和聚合物可涉及天然的或合成的低聚物或聚合物。Oligomers and polymers having H-activated groups can be natural or synthetic oligomers or polymers.
天然的低聚物和聚合物例如是低聚糖和聚糖或其衍生物，肽，蛋白，糖蛋白，酶和生长因子。一些例子是环糊精，淀粉，透明质酸，脱乙酰化的透明质酸，聚氨基葡糖，海藻糖，纤维素三糖，麦芽三糖，麦芽六糖，壳六糖，琼脂糖，壳多糖50，直链淀糖，葡聚糖，肝素木聚糖，果胶，半乳聚糖，聚-半乳糖胺，葡糖胺聚糖，葡聚糖，胺化的葡聚糖，纤维素，羟烷基纤维素，羧基烷基纤维素，肝素，岩藻依聚糖，软骨素硫酸盐，硫酸盐化的聚糖，粘多糖，明胶，酪蛋白，丝心蛋白，玉米醇溶蛋白，胶原，清蛋白，球蛋白，胆红素、卵清蛋白，角蛋白，纤连蛋白和玻连蛋白，胃蛋白酶，胰蛋白酶，溶菌酶。Natural oligomers and polymers are, for example, oligosaccharides and polysaccharides or derivatives thereof, peptides, proteins, glycoproteins, enzymes and growth factors. Some examples are cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, polyglucosamine, trehalose, cellulotriose, maltotriose, maltohexaose, chitohexose, agarose, shell Polysaccharide 50, Amylose, Dextran, Heparin Xylan, Pectin, Galactan, Poly-Galactosamine, Glycosaminoglycan, Dextran, Aminated Dextran, Cellulose , hydroxyalkylcellulose, carboxyalkylcellulose, heparin, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, casein, fibroin, zein, Collagen, albumin, globulin, bilirubin, ovalbumin, keratin, fibronectin and vitronectin, pepsin, trypsin, lysozyme.
合成的低聚物和聚合物可涉及含有基-COOH，-OH，-NH2或-NHRN的物质，其中RN为低级烷基，优选C1-C6-烷基。它例如可涉及乙烯基酯或-醚(聚乙烯醇)的皂化的聚合物，羟基化的聚二烯烃例如聚丁二烯，聚异戊二烯或氯丁二烯；聚丙烯酸和聚甲基丙烯酸以及在酯基或酰胺基中带有羟烷基-或氨基烷基的聚丙烯酸酯，聚甲基丙烯酸酯，聚丙烯酰胺或聚甲基丙烯酰胺；带有羟烷基-或氨基烷基的聚硅氧烷；由环氧化物或缩水甘油基化合物和二醇构成的聚醚；聚乙烯基苯酚或乙烯基苯酚和烯属共聚用单体的共聚物；以及至少由下列组中一种单体与烯属不饱和共聚单体构成的共聚物，其中单体：乙烯基醇，乙烯基吡咯烷酮，丙烯酸，甲基丙烯酸，或含有羟烷基或氨基烷基的丙烯酸酯，甲基丙烯酸酯，或丙烯酰胺或甲基丙烯酰胺，或羟基化的二烯烃，共聚用单体例如丙烯腈，烯烃，二烯烃，氯乙烯，二氯乙烯，氟乙烯，二氟乙烯，苯乙烯，α-甲基苯乙烯，乙烯基醚和乙烯基酯；或涉及带有末端的OH-或氨基烷氧基的聚氧杂亚烷基。Synthetic oligomers and polymers may involve substances containing the group -COOH, -OH, -NH2 or -NHR N , where R N is lower alkyl, preferably C1 - C6 -alkyl. It can concern, for example, saponified polymers of vinyl esters or -ethers (polyvinyl alcohol), hydroxylated polydienes such as polybutadiene, polyisoprene or chloroprene; polyacrylic acid and polymethyl Acrylic acid and polyacrylates, polymethacrylates, polyacrylamides or polymethacrylamides with hydroxyalkyl- or aminoalkyl groups in the ester or amide groups; with hydroxyalkyl- or aminoalkyl groups polysiloxanes; polyethers consisting of epoxides or glycidyl compounds and diols; polyvinylphenol or copolymers of vinylphenol and ethylenic comonomers; and at least one of the following groups Copolymers of monomers and ethylenically unsaturated comonomers, wherein monomers: vinyl alcohol, vinyl pyrrolidone, acrylic acid, methacrylic acid, or acrylates and methacrylates containing hydroxyalkyl or aminoalkyl groups , or acrylamide or methacrylamide, or hydroxylated dienes, comonomers such as acrylonitrile, olefins, dienes, vinyl chloride, vinyl dichloride, vinyl fluoride, vinyl difluoride, styrene, alpha-formaldehyde ylstyrenes, vinyl ethers and vinyl esters; or polyoxyalkylenes with terminal OH- or aminoalkoxy groups.
优选的低聚物和聚合物例如是带有总共6至8形成一个环的葡糖结构单元的环糊精或羟烷基-或氨基烷基衍生物或葡糖-或麦芽糖-取代的衍生物，其中至少一结构单元相当于式(V)，
其他优选的低聚物和聚合物例如是在烷基，烷氧基烷基或氨基亚烷基或其侧链中带有OH-或NH2-基的低硅氧烷或聚硅氧烷。它可涉及无规的或嵌段低聚物或嵌段聚合物。较优选的低聚物和聚合物是这样的化合物，它含有a)5至100mol-％式(VII)结构单元
其他的优选的低聚物和聚合物是以低聚乙烯醇和聚乙烯醇为基础的这种。它涉及具有-CH2CH(OH)-结构单元的均聚物或具有其他单价的或二价的烯烃结构单元的共聚物。Other preferred oligomers and polymers are those based on oligovinyl alcohol and polyvinyl alcohol. It concerns homopolymers with -CH 2 CH(OH)- structural units or copolymers with other monovalent or divalent olefinic structural units.
较优选的是这种低聚物和聚合物，它们含有More preferred are such oligomers and polymers, which contain
a)5至100mol-％式(XI)结构单元
式中R16是RxH基，R17为H，C1-C6-烷基，-COOR20或-COOθ，R18为H，F，Cl，CN或C1-C6-烷基，和R19是H，OH，R10-H，F，Cl，CN，R20-O-，C1-C12-烷基，-COOθ，-COOR20，-OCO-R20，甲基苯基或苯基，其中R10是一直接的键，-(C1-C4-亚烷基-O-)-或-(C2-C10-亚烷基-NH)-并R20为C1-C18-烷基，C5-C7-环烷基，(C1-C12-烷基)-C5-C7-环烷基，苯基，(C1-C12-烷基)苯基，苄基或(C1-C12-烷基)苄基。In the formula, R 16 is R x H group, R 17 is H, C 1 -C 6 -alkyl, -COOR 20 or -COO θ , R 18 is H, F, Cl, CN or C 1 -C 6 -alk radical, and R 19 is H, OH, R 10 -H, F, Cl, CN, R 20 -O-, C 1 -C 12 -alkyl, -COO θ , -COOR 20 , -OCO-R 20 , Methylphenyl or phenyl, wherein R 10 is a direct bond, -(C 1 -C 4 -alkylene-O-)- or -(C 2 -C 10 -alkylene-NH)- and R 20 is C 1 -C 18 -alkyl, C 5 -C 7 -cycloalkyl, (C 1 -C 12 -alkyl)-C 5 -C 7 -cycloalkyl, phenyl, (C 1 - C 12 -alkyl)phenyl, benzyl or (C 1 -C 12 -alkyl)benzyl.
R17优选为H。若R17为烷基，则它优选为甲基或乙基。若R17为-COOR20，则R20优选是C1-C12-，特别是C1-C6-烷基。 R17 is preferably H. If R 17 is alkyl, it is preferably methyl or ethyl. If R 17 is —COOR 20 , R 20 is preferably C 1 -C 12 -, in particular C 1 -C 6 -alkyl.
若R18为烷基，则它优选涉及C1-C4-烷基，例如甲基，乙基，n-丙基或n-丁基。R18优选为H，Cl或C1-C4-烷基。If R 18 is alkyl, it is preferably a C 1 -C 4 -alkyl group, for example methyl, ethyl, n-propyl or n-butyl. R 18 is preferably H, Cl or C 1 -C 4 -alkyl.
若R19为基R20-O-，则R20优选是C1-C12-，特别是C1-C6-烷基。若R19为烷基，则它优选含有1至6，特别是1至4C-原子。若R19为基-COOR20，则R20优选是C1-C12-，特别是C1-C6-烷基，环戊基或环己基。若R19为基-OCO-R20，则R20优选是C1-C12-，特别是C1-C6-烷基，苯基或苄基。If R 19 is a radical R 20 -O—, R 20 is preferably C 1 -C 12 -, in particular C 1 -C 6 -alkyl. If R 19 is alkyl, it preferably contains 1 to 6, especially 1 to 4, C-atoms. If R 19 is a group -COOR 20 , R 20 is preferably C 1 -C 12 -, in particular C 1 -C 6 -alkyl, cyclopentyl or cyclohexyl. If R 19 is a group -OCO-R 20 , R 20 is preferably C 1 -C 12 -, in particular C 1 -C 6 -alkyl, phenyl or benzyl.
在一优选的实施方案中R17为H，R18为H，F，Cl，甲基或乙基，和R19为H，OH，F，Cl，CN，C1-C4-烷基，C1-C6-烷氧基，C1-C6-羟基烷氧基，-COO-C1-C6-烷基，-OOC-C1-C6-烷基或苯基。In a preferred embodiment R 17 is H, R 18 is H, F, Cl, methyl or ethyl, and R 19 is H, OH, F, Cl, CN, C 1 -C 4 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -hydroxyalkoxy, -COO-C 1 -C 6 -alkyl, -OOC-C 1 -C 6 -alkyl or phenyl.
特别优选是这种低聚物和聚合物，式中R17为H，R18是H或甲基，和R19为H，OH，CN，甲基，OCH3，O(CH2)tOH或-COOCH3，和t为2至6的整数。Especially preferred are such oligomers and polymers in which R 17 is H, R 18 is H or methyl, and R 19 is H, OH, CN, methyl, OCH 3 , O(CH 2 ) t OH or -COOCH 3 , and t is an integer from 2 to 6.
低聚物和聚合物另一优选组是部分地或完全羟基烷基化的低聚或聚丙烯酸酯或-甲基丙烯酸酯或-丙烯酰胺或-甲基丙烯酰胺。它们可含有例如5至100mol-％式(XIII)结构单元。
其他优选的低聚物和聚合物是由聚烯化氧组成的这种。它可涉及例如具有相同的或不同的重复结构单元-〔CH2CH(R26)-O〕-的式(XV)的这种，
式中R25是基R28-X4-或具有1至20C-原子的醇或多元醇的基(其中此基的价为1至v)，R26为H，C1-C8-烷基，优选C1-C4-烷基和特别优选为甲基，R27与X4一起是一直接的键或R27是C2-C6-亚烷基，优选C3-C6-亚烷基和特别优选1，3-亚丙基，X4为-O-或-NH-，R28为式RxH的基，u为3至10,000的一数值，优选5至5000，特别优选5至1000和最优选5至100，和v为1至6的一个整数，优选1至4。In the formula, R 25 is a radical R 28 -X 4 - or a radical of an alcohol or polyol having 1 to 20 C-atoms (wherein the radical has a valency of 1 to v), R 26 is H, C 1 -C 8 -alk radical, preferably C 1 -C 4 -alkyl and particularly preferably methyl, R 27 together with X 4 is a direct bond or R 27 is C 2 -C 6 -alkylene, preferably C 3 -C 6 - Alkylene and particularly preferably 1,3-propylene, X 4 is -O- or -NH-, R 28 is a radical of the formula R x H, u is a value from 3 to 10,000, preferably from 5 to 5000, especially Preferably 5 to 1000 and most preferably 5 to 100, and v is an integer from 1 to 6, preferably 1 to 4.
R25可以是醇或多元醇的一至四价的基。若R25涉及醇的基时，则R25优选为直链的或支链的-C3-C20-烷基或-链烯基，C3-C8-和特别是C5-C6-环烷基，-CH2-(C5-C6-环烷基)，C6-C10-芳基和特别是苯基和萘基，C7-C16-芳烷基和特别是苄基和1-苯基乙-2-基。这些环的或芳族的基可以是以C1-C18-烷基或C1-C18-烷氧基取代的。R 25 may be a mono- to tetravalent group of alcohol or polyol. If R 25 is an alcohol radical, R 25 is preferably a linear or branched -C 3 -C 20 -alkyl or -alkenyl, C 3 -C 8 - and especially C 5 -C 6 -cycloalkyl, -CH 2 -(C 5 -C 6 -cycloalkyl), C 6 -C 10 -aryl and especially phenyl and naphthyl, C 7 -C 16 -aralkyl and especially Benzyl and 1-phenyleth-2-yl. These cyclic or aromatic radicals may be substituted by C 1 -C 18 -alkyl or C 1 -C 18 -alkoxy.
若R25涉及二醇的基时，则R25优选为支链的和特别是直链的C3-C20-亚烷基或亚链烯基和较优选C3-C12-亚烷基，C3-C8-和特别是C5-C6-亚环烷基，-CH2-(C5-C6-环烷基)-，-CH2-(C5-C6-环烷基)-CH2-，C7-C16-芳亚烷基和特别是亚苄基，-CH2-(C6-C10-芳基)-CH2-和特别是亚二甲苯基。这些环的或芳族的基可以是以C1-C12-烷基或C1-C12-烷氧基取代的。If R 25 is a diol radical, R 25 is preferably branched and especially straight-chain C 3 -C 20 -alkylene or alkenylene and more preferably C 3 -C 12 -alkylene , C 3 -C 8 - and especially C 5 -C 6 -cycloalkylene, -CH 2 -(C 5 -C 6 -cycloalkyl)-, -CH 2 -(C 5 -C 6 -cycloalkylene Alkyl)-CH 2 -, C 7 -C 16 -aralkylene and especially benzylidene, -CH 2 -(C 6 -C 10 -aryl)-CH 2 - and especially xylylene . These cyclic or aromatic radicals may be substituted by C 1 -C 12 -alkyl or C 1 -C 12 -alkoxy.
若R25涉及-个三价基时，则此基来自脂族的或芳族的三醇。R25优选是一个三价的脂族的具有3至12C-原子的基，它特别来自具有优选伯羟基的三醇。特别优选R25是-CH2(CH-)CH2-，HC(CH2-)3或CH3-C(CH2-)3。If R 25 involves a trivalent group, this group is derived from an aliphatic or aromatic triol. R 25 is preferably a trivalent aliphatic radical having 3 to 12 C-atoms, in particular from a triol with preferably primary hydroxyl groups. Particularly preferably R 25 is —CH 2 (CH—)CH 2 —, HC(CH 2 —) 3 or CH 3 —C(CH 2 —) 3 .
若R25涉及一个四价基时，则此基优选来自脂族的四醇。R25在这种情况是优选C(CH2-)4。If R 25 is a tetravalent radical, this radical is preferably derived from an aliphatic tetraol. R 25 is in this case preferably C(CH 2 −) 4 .
R25优选为一来自Jeffamine(Texaco)，一种Pluriol，一种Poloxamer(BASF)或聚(四氢呋喃)的基。 R25 is preferably a radical derived from Jeffamine (Texaco), a Pluriol, a Poloxamer (BASF) or poly(tetrahydrofuran).
特别优选是具有式-〔CH2CH2-O-〕-或-〔CH2CH(CH3)-O〕-结构单元的均-和嵌段低聚物和均-和嵌段聚合物。Particular preference is given to homo- and block oligomers and homo- and block polymers having structural units of the formula -[CH 2 CH 2 -O-]- or -[CH 2 CH(CH3 ) -O]-.
相当于式(XVI)的氟化的聚醚也是适合的，
另外适宜的低聚物和聚合物例如是聚胺如聚乙烯基胺或聚亚乙基亚胺。同样适宜的是聚-ε赖氨酸。Further suitable oligomers and polymers are, for example, polyamines such as polyvinylamine or polyethyleneimine. Also suitable is poly-εlysine.
作为式B的光引发剂原则上是每种含异氰酸酯基的光引发剂都适宜。这类的光引发剂例如是在EP-A-632329中已记述的。适宜的光引发剂通常具有这种结构单元
(其中式子“OH/NR’R””表示，有关的碳原子或带有OH-基或带有NR’R”-基，式中R’和R”相互独立地为直链的或支链的低级烷基(它可以是以C1-C4-烷氧基取代的)，芳基低级烷基或低级链烯基；或R’和R”一起为-(CH2)z-Y11-(CH2)z-，其中Y11是一直接的键，-O-，-S-，或-NR1B-和R1B为H或低级烷基和z为2至4的一个整数)，它在激发时形成二个自由基，方法是：分裂苯甲酰基碳和sp3-碳之间的键。通常是此苯甲酰基是更具反应性的，它总能使聚合开始。因此式B的变量PI*优选相当于这类的苯甲酰自由基。这种苯甲酰自由基如在现有技术中已知是被取代的并含有按本发明的附加的一异氰酸酯基。由前面可得出，此sp3-碳自由基是弱反应的，它通常不能使聚合开始。代替这种情况它优选作为链终止剂进行反应。因此式B的变量Raa优选相当于一种这类的sp3-碳自由基。(The formula "OH/NR'R"" means that the relevant carbon atoms either have OH-groups or NR'R"-groups, where R' and R" are independently linear or branched chain lower alkyl (which may be substituted with C 1 -C 4 -alkoxy), aryl lower alkyl or lower alkenyl; or R' and R" together are -(CH 2 ) z -Y 11 -(CH 2 ) z -, wherein Y 11 is a direct bond, -O-, -S-, or -NR 1B - and R 1B is H or lower alkyl and z is an integer from 2 to 4) , which upon excitation forms two free radicals by cleaving the bond between the benzoyl carbon and the sp 3 -carbon. Usually this benzoyl group is the more reactive, it always starts the polymerization. The variable PI * of formula B therefore preferably corresponds to a benzoyl radical of this type. This benzoyl radical is substituted as known in the prior art and contains an additional monoisocyanate group according to the invention. From the foregoing it can be concluded that this sp 3 -carbon radical is weakly reactive, it generally cannot initiate polymerization. Instead it preferably reacts as a chain terminator. The variable R aa of formula B therefore preferably corresponds to one such sp 3 -carbon radical.
特别优选的本发明的光引发剂描述如下。Particularly preferred photoinitiators of the invention are described below.
本发明使用的官能的式B光引发剂优选是式IIa或IIb化合物
在一优选实施方案中Y为O。In a preferred embodiment Y is O.
R1A作为烷基例如可以是甲基，乙基，n-或i-丙基，n-，i-或t-丁基，戊基或己基。R1A优选是甲基。R 1A as alkyl can be, for example, methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl or hexyl. R 1A is preferably methyl.
基R作为烷基，烷氧基或烷基NH-优选含有1至6和特别优选1至4C-原子。一些例子是甲基，乙基，n-或i-丙基，n-，i-或t-丁基，戊基，己基，辛基，癸基，十二烷基，甲氧基，乙氧基，丙氧基，丁氧基和甲基NH-。特别优选R为H。The radical R as alkyl, alkoxy or alkyl NH- preferably contains 1 to 6 and particularly preferably 1 to 4 C-atoms. Some examples are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy radical, propoxy, butoxy and methyl NH-. It is particularly preferred that R is H.
R1作为烷基优选直链的和含有优选1至4C-原子。一些例子是甲基，乙基，n-或i-丙基，n-，i-或t-丁基，戊基，己基，庚基和辛基。R1特别优选涉及甲基或乙基。R1作为芳基例如可为萘基和特别为苯基。若二个基R1-(Y1)n-一起为-(CH2)x-，则x优选是4并特别优选5。R1作为羟烷基优选是直链的并含有优选1至4C-原子。一些例子是羟甲基，2-羟基乙-1-基。R 1 as alkyl is preferably straight-chain and contains preferably 1 to 4 C-atoms. Some examples are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, heptyl and octyl. R 1 is particularly preferably methyl or ethyl. R 1 as aryl can be, for example, naphthyl and especially phenyl. If two radicals R 1 -(Y 1 ) n - together are -(CH 2 ) x -, then x is preferably 4 and particularly preferably 5. R 1 as hydroxyalkyl is preferably straight-chain and contains preferably 1 to 4 C-atoms. Some examples are hydroxymethyl, 2-hydroxyeth-1-yl.
对R2适用与R1相同的优选情况。R2特别优选为H，甲基或乙基。The same preferences as for R1 apply to R2 . R2 is particularly preferably H, methyl or ethyl.
Ra和Rb相互独立地优选为H或C1-C4-烷基，例如甲基或乙基。Ra and Rb are independently of one another preferably H or C 1 -C 4 -alkyl, eg methyl or ethyl.
在一优选的次组中R1优选为乙基和特别优选甲基或二个基R1-(Y1)n-一起为五亚甲基，n在基-(Y1)n-R2中优选为0，R2优选是甲基，羟甲基或H和R为H。In a preferred subgroup R 1 is preferably ethyl and particularly preferably methyl or the two radicals R 1 -(Y 1 ) n - together are pentamethylene, n is in the radical -(Y 1 ) n -R 2 In is preferably 0, R2 is preferably methyl, hydroxymethyl or H and R is H.
在另一优选实施方案中在基-(Y1)n-R2中Y1为O，n为1和R2为H。尤其是在这种情况在基R1-(Y1)n-中n为O。In another preferred embodiment Y 1 is O, n is 1 and R 2 is H in the group -(Y 1 ) n -R 2 . In particular in this case n is O in the group R 1 -(Y 1 ) n -.
R3作为亚烷基优选含有1至6和特别优选1至4C-原子和亚烷基优选是直链的。一些例子是亚甲基，亚乙基，1，2-或1，3-亚丙基，1，2-1，3-或1，4-亚丁基，亚戊基，亚己基，亚庚基和亚辛基。优选是亚甲基，亚乙基，1，3-亚丙基和1，4-亚丁基。最优选R3是亚乙基；或一直接的键，其中n在基-(Y2)n-中为0。R 3 as alkylene preferably contains 1 to 6 and particularly preferably 1 to 4 C-atoms and the alkylene is preferably straight-chain. Some examples are methylene, ethylene, 1,2- or 1,3-propylene, 1,2-1,3- or 1,4-butylene, pentylene, hexylene, heptylene and Yasinki. Preferred are methylene, ethylene, 1,3-propylene and 1,4-butylene. Most preferably R3 is ethylene; or a direct bond wherein n is 0 in the group -( Y2 ) n- .
R3作为以羟基取代的亚烷基可涉及例如特别是2-羟基-1，3-亚丙基或也涉及2-羟基-1，3-或-1，4-亚丁基。用-O-间断的和必要时用-OH取代的亚烷基例如是-CH2CH2-O-CH2CH2-，-CH2CH2-O-CH2CH2-O-CH2CH2-，-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-，[CH(CH3)CH2-，O-CH(CH 3 )CH 2 -]R 3 as hydroxy-substituted alkylene can be, for example, in particular 2-hydroxy-1,3-propylene or also 2-hydroxy-1,3- or -1,4-butylene. Alkylene interrupted by -O- and optionally substituted by -OH is for example -CH 2 CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -, [CH(CH 3 )CH 2 -,O-CH(CH 3 )CH 2- ]
-CH(CH3)CH2-O-CH2CH2-，-CH(C2H5)CH2-O-CH2CH2-，-CH(CH 3 )CH 2 -O-CH 2 CH 2 -, -CH(C 2 H 5 )CH 2 -O-CH 2 CH 2 -,
[-CH(C2H5)CH2-O-CH(C2H5)CH2-]或-CH2CH2CH2CH2-O-CH2CH2CH2CH2-和-CH2CH(OH)CH2-O-CH2CH2-.以-O-C(O)-或-C(O)-O-间断的亚烷基例如是-CH2CH2-C(O)-O-CH2-或-CH2CH2-O-C(O)-CH2-.以-O-C(O)-O-间断的亚烷基例如是-CH2CH2-O-C(O)-O-CH2CH2-或CH2CH2-O-C(O)-O-CH2-.[-CH(C 2 H 5 )CH 2 -O-CH(C 2 H 5 )CH 2 -] or -CH 2 CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 - and -CH 2 CH(OH)CH 2 -O-CH 2 CH 2 -. The alkylene group interrupted by -OC(O)- or -C(O)-O- is, for example, -CH 2 CH 2 -C(O)- O-CH 2 - or -CH 2 CH 2 -OC(O)-CH 2 -. The alkylene group interrupted by -OC(O)-O- is, for example, -CH 2 CH 2 -OC(O)-O- CH 2 CH 2 - or CH 2 CH 2 -OC(O)-O-CH 2 -.
取代基C1-C4-烷基和C1-C4-烷氧基优选涉及甲基，乙基，甲氧基或乙氧基。The substituents C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy are preferably methyl, ethyl, methoxy or ethoxy.
R4作为支链的亚烷基优选含有3至14和特别优选4至10C-原子。亚烷基的例子是1，2-亚丙基，2-甲基-或2，2-二甲基-1，3-亚丙基，1，2-，1，3-和2，3-亚丁基，2-甲基-或2，3-二甲基-1，4-亚丁基，1，2-，1，3-或1，4-亚戊基，2-甲基-或3-甲基-或4-甲基-或2，3-二甲基-或2，4-二甲基-或3，4-二甲基-或2，3，4-三甲基-2，2，3-三甲基-或2，2，4-三甲基-或2，2，3，3-四甲基-或2，2，3，4-四甲基-1，5-亚戊基，1，2-，1，3-，1，4-或1，5-亚己基，2-甲基-或3-甲基-或4-甲基-或2，2-二甲基-或3，3-二甲基-或2，3-二甲基-或2，4-二甲基-或3， 4-二甲基-或2，2，3-三甲基-或2，2，4-三甲基-或2，2，5-三甲基-或2，3，4-三甲基-或2，2，4，5-四甲基-1，6-亚己基。其他的例子是在EP-A-632329中公开的。R 4 preferably contains 3 to 14 and particularly preferably 4 to 10 C-atoms as branched alkylene. Examples of alkylene groups are 1,2-propylene, 2-methyl- or 2,2-dimethyl-1,3-propylene, 1,2-, 1,3- and 2,3- Butylene, 2-methyl- or 2,3-dimethyl-1,4-butylene, 1,2-, 1,3- or 1,4-pentylene, 2-methyl- or 3- Methyl- or 4-methyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,3,4-trimethyl-2,2 , 3-trimethyl-or 2,2,4-trimethyl-or 2,2,3,3-tetramethyl-or 2,2,3,4-tetramethyl-1,5-pentylene 1,2-, 1,3-, 1,4- or 1,5-hexylene, 2-methyl- or 3-methyl- or 4-methyl- or 2,2-dimethyl- or 3,3-dimethyl- or 2,3-dimethyl- or 2,4-dimethyl- or 3,4-dimethyl- or 2,2,3-trimethyl- or 2, 2,4-trimethyl- or 2,2,5-trimethyl- or 2,3,4-trimethyl- or 2,2,4,5-tetramethyl-1,6-hexylene. Other examples are disclosed in EP-A-632329.
一些优选的支链的亚烷基是2，2-二甲基-1，4-亚丁基，2，2-二甲基-1，5-亚戊基，2，2，3-三甲基-1，5-亚戊基，2，2-二甲基-1，6-亚己基，2，2，3-或2，2，4-或2，2，5-三甲基-1，6-亚己基，2，2-二甲基-1，7-亚庚基，2，2，3-或2，2，4-或2，2，5-或2，2，6-三甲基-1，7-亚庚基，2，2-二甲基-1，8亚辛基，2，2，3-或2，2，4-或2，2，5-或2，2，6-或2，2，7-三甲基-1，8-亚辛基。Some preferred branched chain alkylene groups are 2,2-dimethyl-1,4-butylene, 2,2-dimethyl-1,5-pentylene, 2,2,3-trimethyl -1,5-pentylene, 2,2-dimethyl-1,6-hexylene, 2,2,3- or 2,2,4- or 2,2,5-trimethyl-1, 6-hexylene, 2,2-dimethyl-1,7-heptylene, 2,2,3-or 2,2,4-or 2,2,5-or 2,2,6-trimethyl Base-1,7-heptylene, 2,2-dimethyl-1,8-octylene, 2,2,3-or 2,2,4-or 2,2,5-or 2,2, 6- or 2,2,7-trimethyl-1,8-octylene.
若R4是亚芳基时，则优选涉及亚萘基和特别优选涉及亚苯基。若此亚芳基是被取代的时，则取代基优选处在异氰酸酯基的邻位上。取代的亚芳基的例子是1-甲基-2，4-亚苯基，1，5-二甲基-2，4-亚苯基，1-甲氧基-2，4-亚苯基和1-甲基-2，7-亚萘基。If R 4 is arylene, it is preferably naphthylene and particularly preferably phenylene. If the arylene group is substituted, the substituent is preferably in the ortho position to the isocyanate group. Examples of substituted arylene groups are 1-methyl-2,4-phenylene, 1,5-dimethyl-2,4-phenylene, 1-methoxy-2,4-phenylene and 1-methyl-2,7-naphthylene.
R4作为芳亚烷基优选是萘基亚烷基和特别优选苯基亚烷基。在芳亚烷基中的亚烷基优选含有1至12，特别优选1至6和尤其是优选1至4C-原子。在芳亚烷基中的亚烷基最优选是亚甲基或亚乙基。一些例子是1，3-或1，4-亚苄基，萘-2-基-7-亚甲基，6-甲基-1，3-或-1，4-亚苄基，6-甲氧基-1，3-或1，4-亚苄基。R 4 as aralkylene is preferably naphthylalkylene and particularly preferably phenylalkylene. The alkylene group in the aralkylene group preferably contains 1 to 12, particularly preferably 1 to 6 and especially preferably 1 to 4 C-atoms. The alkylene group in the aralkylene group is most preferably methylene or ethylene. Some examples are 1,3- or 1,4-benzylidene, naphthalene-2-yl-7-methylene, 6-methyl-1,3-or-1,4-benzylidene, 6-methyl Oxy-1,3- or 1,4-benzylidene.
若R4是亚环烷基时，则优选涉及C5-或C6-亚环烷基，它是未取代的或以甲基取代的。一些例子是1，3-亚环丁基，1，3-亚环戊基，1，3-或1，4-亚环己基，1，3-或1，4-亚环庚基，1，3-或1，4-或1，5-亚环辛基，4-甲基-1，3-亚环戊基，4-甲基-1，3-亚环己基，4，4-二甲基-1，3-亚环己基，3-甲基-或3，3-二甲基-1，4-亚环己基，3，5-二甲基-1，3-亚环己基，2，4-二甲基-1，4-亚环己基。If R 4 is cycloalkylene, it is preferably C 5 - or C 6 -cycloalkylene, which is unsubstituted or substituted with methyl. Some examples are 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3- or 1,4-cyclohexylene, 1,3- or 1,4-cycloheptylene, 1, 3- or 1,4- or 1,5-cyclooctylene, 4-methyl-1,3-cyclopentylene, 4-methyl-1,3-cyclohexylene, 4,4-dimethyl Base-1,3-cyclohexylene, 3-methyl- or 3,3-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,3-cyclohexylene, 2, 4-Dimethyl-1,4-cyclohexylene.
若R4为亚环烷基-CyH2y-时，则优选涉及亚环戊基-CyH2y-和特别涉及亚环己基-CyH2y-，它是未取代的或优选以1至3个C1-C4-烷基，特别优选甲基，取代的。在基-CyH2y-中优选y为1至4的整数。更优选基-CyH2y-是亚乙基和特别优选亚甲基。一些例子是环戊-1-基-3-亚甲基，3-甲基-环戊-1-基-3-亚甲基，3，4-二甲基-环戊-1-基-3-亚甲基，3，4，4-三甲基-环戊-1-基-3-亚甲基，环己-1-基-3-或-4-亚甲基，3-或4-或5-甲基-环己-1-基-3-或-4-亚甲基，3，4-或3，5-二甲基-环己-1-基-3-或-4-亚甲基，3，4，5-或3，4，4-或3，5，5-三甲基-环己-1-基-3-或-4-亚甲基。When R 4 is cycloalkylene-C y H 2y -, it is preferably cyclopentylene-C y H 2y- and in particular cyclohexylene-C y H 2y- , which is unsubstituted or preferably represented by 1 to 3 C 1 -C 4 -alkyl, particularly preferably methyl, substituted. In the group -C y H 2y - preferably y is an integer from 1 to 4. More preferably the radical -CyH2y- is ethylene and particularly preferably methylene. Some examples are cyclopent-1-yl-3-methylene, 3-methyl-cyclopent-1-yl-3-methylene, 3,4-dimethyl-cyclopent-1-yl-3 -methylene, 3,4,4-trimethyl-cyclopent-1-yl-3-methylene, cyclohex-1-yl-3- or -4-methylene, 3- or 4- Or 5-methyl-cyclohex-1-yl-3-or-4-methylene, 3,4-or 3,5-dimethyl-cyclohex-1-yl-3-or-4-methylene Methyl, 3,4,5- or 3,4,4- or 3,5,5-trimethyl-cyclohex-1-yl-3-or-4-methylene.
若R4为-CyH2y-亚环烷基-CyH2y-时，则优选涉及-CyH2y-亚环戊基-CyH2y-和特别涉及-CyH2y-亚环己基-CyH2y-，它是未取代的或优选以1至3个C1-C4-烷基，特别优选甲基，取代的。在基-CyH2y-中y优选为1至4的整数。基-CyH2y-更优选为亚乙基和特别优选为亚甲基。一些例子是环戊烷-1，3-二亚甲基，3-甲基-环戊烷-1，3-二亚甲基，3，4-二甲基-环戊烷-1，3-二亚甲基，3，4，4-三甲基-环戊烷-1，3-二亚甲基，环己烷-1，3-或-1，4-二亚甲基，3-或4-或5-甲基-环己烷-1，3-或-1，4-二亚甲基，3，4-或3，5-二甲基-环己烷-1，3-或-1，4-二亚甲基，3，4，5-或3，4，4-或3，5，5-三甲基-环己烷-1，3-或1，4-二亚甲基。When R 4 is -C y H 2y -cycloalkylene-C y H 2y -, it preferably relates to -C y H 2y -cyclopentylene-C y H 2y - and in particular relates to -C y H 2y - Cyclohexylene- CyH2y- , which is unsubstituted or substituted preferably with 1 to 3 C1 - C4 - alkyl, particularly preferably methyl. In the group -C y H 2y - y is preferably an integer from 1 to 4. The group -C y H 2y - is more preferably ethylene and particularly preferably methylene. Some examples are cyclopentane-1,3-dimethylene, 3-methyl-cyclopentane-1,3-dimethylene, 3,4-dimethyl-cyclopentane-1,3- Dimethylene, 3,4,4-trimethyl-cyclopentane-1,3-dimethylene, cyclohexane-1,3-or-1,4-dimethylene, 3-or 4- or 5-methyl-cyclohexane-1,3-or-1,4-dimethylene, 3,4- or 3,5-dimethyl-cyclohexane-1,3-or- 1,4-dimethylene, 3,4,5- or 3,4,4-or 3,5,5-trimethyl-cyclohexane-1,3- or 1,4-dimethylene .
若R5具有如R4相同的含义时，则前面对R4陈述的优选情况也适用。R5作为直链的亚烷基优选含有3至12和特别优选3至8C-原子，一些直链亚烷基的例子是1，3-亚丙基，1，4-亚丁基，1，5-亚戊基，1，6-亚己基，1，7-亚庚基，1，8-亚辛基，1，9-亚壬基，1，10-亚癸基，1，11-亚十一烷基，1，12-亚十二烷基，1，14-亚十四烷基，1，18-亚十八烷基。If R 5 has the same meaning as R 4 , the preferences stated above for R 4 also apply. R 5 as straight-chain alkylene preferably contains 3 to 12 and particularly preferably 3 to 8 C-atoms, examples of some straight-chain alkylene are 1,3-propylene, 1,4-butylene, 1,5 -Pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-decylene Monoalkyl, 1,12-dodecylene, 1,14-tetradecylene, 1,18-octadecylene.
X的优选含义是-O-，-NH-，-S-或低级亚烷基。更优选X为-O-或-S-和特别优选为-O-。A preferred meaning of X is -O-, -NH-, -S- or lower alkylene. More preferably X is -O- or -S- and particularly preferably -O-.
在一优选Y10含义中角标y为1-5，更优选为2-4和最优选为2-3，因此Y10例如为亚乙氧基或亚丙氧基。在一另外优选含义中Y10为一直接的键，其中X是或含有优选至少一杂原子。In a preferred meaning of Y 10 the subscript y is 1-5, more preferably 2-4 and most preferably 2-3, so Y 10 is, for example, ethyleneoxy or propyleneoxy. In a further preferred meaning Y 10 is a direct bond, wherein X is or contains preferably at least one heteroatom.
基R100作为烷基，烷氧基，烷基NH-或-NR1AB1B含有优选1至6和特别优选1至4C-原子。一些例子是甲基，乙基，n-或i-丙基，n-，i-或t-丁基，戊基，己基，辛基，癸基，十二烷基，甲氧基，乙氧基，丙氧基，丁氧基，N，N-二甲基氨基和N-甲基氨基。特别优选R为H。一优选的-NR1AR1B含义是N，N-二甲基氨基，N-甲基氨基，N-甲基-N-乙基氨基，N-乙基氨基，N，N-二乙基氨基，N-异丙基氨基或N，N-二异丙基氨基。The radical R 100 as alkyl, alkoxy, alkyl NH- or -NR 1A B 1B contains preferably 1 to 6 and particularly preferably 1 to 4 C-atoms. Some examples are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy radical, propoxy, butoxy, N,N-dimethylamino and N-methylamino. It is particularly preferred that R is H. A preferred meaning of -NR 1A R 1B is N, N-dimethylamino, N-methylamino, N-methyl-N-ethylamino, N-ethylamino, N, N-diethylamino , N-isopropylamino or N,N-diisopropylamino.
R101优选为烯丙基，苄基，直链的C1-C4-烷基例如甲基或乙基。R 101 is preferably allyl, benzyl, straight-chain C 1 -C 4 -alkyl such as methyl or ethyl.
R102优选具有如R101相同的含义，更优选是直链的具有1至4C-原子的和特别优选1至2C-原子的低级烷基。R102作为芳基例如可以为萘基或特别为苯基，它是未取代的或通过低级烷基或低级烷氧基取代的。若R101和R102一起为-(CH2)m-时，则m优选是4或5和特别优选5。R 102 preferably has the same meaning as R 101 , more preferably straight-chain lower alkyl having 1 to 4 C-atoms and particularly preferably 1 to 2 C-atoms. R 102 as aryl can be, for example, naphthyl or especially phenyl, which is unsubstituted or substituted by lower alkyl or lower alkoxy. If R 101 and R 102 together are -(CH 2 ) m -, m is preferably 4 or 5 and particularly preferably 5.
R103优选为直链的具有1至4C-原子的低级烷基，苄基或烯丙基和更优选甲基或乙基。R 103 is preferably straight-chain lower alkyl having 1 to 4 C-atoms, benzyl or allyl and more preferably methyl or ethyl.
R104优选为直链的具有1至4C-原子的低级烷基，和更优选甲基或乙基。R 104 is preferably a linear lower alkyl group having 1 to 4 C-atoms, and more preferably methyl or ethyl.
若R103和R104一起为-(CH2)z-Y11-(CH2)z-时，则Y11优选为一直接的键，-O-或-N(CH3)-和最优选-O-；z优选是2-3和特别优选2。If R 103 and R 104 together are -(CH 2 ) z -Y 11 -(CH 2 ) z -, then Y 11 is preferably a direct bond, -O- or -N(CH 3 )- and most preferably -O-; z is preferably 2-3 and 2 is particularly preferred.
式IIa化合物的优选次组是这样的化合物，式中在基R1-(Y1)n-中n为0，在基R2-(Y1)n-中Y，Y2和Y1各为O，n在基R2-(Y1)n-中为0或1，R1为C1-C4-烷基或苯基或基R1-(Y1)n -一起是四亚甲基或五亚甲基，R2是C1-C4-烷基或H，R为氢，n在基-(Y2)n-中为0或1，R3是直链的或支链的C2-C4-亚烷基或为一直接的键，其中n在基-(Y2)n-中为0，R4为支链的C5-C10-亚烷基，亚苯基或以1至3个甲基取代的亚苯基，亚苄基或以1至3甲基取代的亚苄基，亚环己基或以1至3甲基取代的亚环己基，环己基-CyH2y-或-CyH2y-环己基-CyH2y-或以1至3个甲基取代的环己基-CyH2y-或-CyH2y-环己基-CyH2y-，R5具有对R4已陈述的含义或是直链的C3-C10-亚烷基，和y为1或2。A preferred subgroup of compounds of formula IIa are compounds wherein n in the group R 1 -(Y 1 ) n - is 0, and in the group R 2 -(Y 1 ) n - Y, Y 2 and Y 1 are each is O, n is 0 or 1 in the group R 2 -(Y 1 ) n -, R 1 is C 1 -C 4 -alkyl or phenyl or the group R 1 -(Y 1 ) n - together are tetraethylene Methyl or pentamethylene, R 2 is C 1 -C 4 -alkyl or H, R is hydrogen, n is 0 or 1 in the group -(Y 2 ) n -, R 3 is linear or branched chain C 2 -C 4 -alkylene or a direct bond, wherein n is 0 in the group -(Y 2 ) n -, R 4 is a branched C 5 -C 10 -alkylene, alkylene Phenyl or phenylene substituted with 1 to 3 methyl groups, benzylidene or benzylidene substituted with 1 to 3 methyl groups, cyclohexylene or cyclohexylene substituted with 1 to 3 methyl groups, cyclohexyl -C y H 2y -or -C y H 2y -cyclohexyl-C y H 2y -or cyclohexyl substituted with 1 to 3 methyl groups-C y H 2y -or -C y H 2y -cyclohexyl-C y H 2y -, R 5 has the meanings already stated for R 4 or is straight-chain C 3 -C 10 -alkylene, and y is 1 or 2.
式IIa化合物特别优选的次组是这样的化合物，式中在基R1-(Y1)n-和-(Y2)n-中n为0，在基R2-(Y1)n-中Y，Y2和Y1各为O，n在基R2-(Y1)n-中为0或1，R1为甲基或苯基或基R1-(Y1)n-一起是五亚甲基，R2是甲基或H，R为氢，n在基-(Y2)n-中为1和R3是亚乙基或n在基-(Y2)n-中为0和R3为一直接的键，R4为支链的C6-C10-亚烷基，亚苯基或以1至3个甲基取代的亚苯基，亚苄基或以1至3个甲基取代的亚苄基，亚环己基或以1至3个甲基取代的亚环己基，环己基-CH2-或以1至3个甲基取代的环己基-CH2-，和R5具有对R4陈述过的含义或是直链的C5-C10-亚烷基。A particularly preferred subgroup of compounds of formula IIa are those compounds in which n is 0 in the radicals R 1 -(Y 1 ) n - and -(Y 2 ) n -, and in the radicals R 2 -(Y 1 ) n - Y, Y 2 and Y 1 are each O, n is 0 or 1 in the group R 2 -(Y 1 ) n -, R 1 is methyl or phenyl or the group R 1 -(Y 1 ) n - together is pentamethylene, R 2 is methyl or H, R is hydrogen, n is 1 in the group -(Y 2 ) n - and R 3 is ethylene or n in the group -(Y 2 ) n - is 0 and R 3 is a direct bond, R 4 is branched C 6 -C 10 -alkylene, phenylene or phenylene substituted with 1 to 3 methyl groups, benzylidene or 1 Benzylene substituted with 3 methyl groups, cyclohexylene or cyclohexylene substituted with 1 to 3 methyl groups, cyclohexyl-CH 2 - or cyclohexyl substituted with 1 to 3 methyl groups-CH 2 - , and R 5 has the meanings stated for R 4 or is straight-chain C 5 -C 10 -alkylene.
式IIb化合物优选的次组是这样的化合物，式中R101为直链的低级烷基，低级链烯基或芳基低级烷基；R102与R101无关具有如R101相同的含义或为芳基；R103和R104相互独立地为直链的或支链的低级烷基(它可以是以C1-C4-烷氧基取代的)，芳基低级烷基或低级链烯基；或R103和R104一起为-(CH2)z-Y11-(CH2)z-，其中Y11是一直接的键，-O-，-S-，或-NR1B-和R1B为H或低级烷基和z为2至4的一个整数；和R5为直链的或支链的C3-C18-亚烷基，未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的C6-C10-亚芳基，或未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的C7-C18-芳亚烷基，未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的C13-C24-亚芳基亚烷基亚芳基，未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的C3-C8-亚环烷基，未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的C3-C8-亚环烷基-CyH2y-或未取代的或以C1-C4-烷基或C1-C4-烷氧基取代的-CyH2y-(C3-C8-亚环烷基)-CyH2y-，其中y为1-6的一个整数。A preferred subgroup of compounds of formula IIb are compounds wherein R 101 is a linear lower alkyl, lower alkenyl or aryl lower alkyl; R 102 has the same meaning as R 101 regardless of R 101 or is Aryl; R 103 and R 104 are independently of each other linear or branched lower alkyl (which may be substituted with C 1 -C 4 -alkoxy), aryl lower alkyl or lower alkenyl ; or R 103 and R 104 together are -(CH 2 ) z -Y 11 -(CH 2 ) z -, wherein Y 11 is a direct bond, -O-, -S-, or -NR 1B -and R 1B is H or lower alkyl and z is an integer from 2 to 4; and R is linear or branched C 3 -C 18 -alkylene, unsubstituted or C 1 -C 4 -alkane or C 1 -C 4 -alkoxy substituted C 6 -C 10 -arylene, or unsubstituted or C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy substituted C 7 -C 18 -aralkylene, unsubstituted or C 13 -C 24 -arylenealkylenearylene substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy , unsubstituted or C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy substituted C 3 -C 8 -cycloalkylene, unsubstituted or C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy substituted C 3 -C 8 -cycloalkylene-C y H 2y -or unsubstituted or C 1 -C 4 -alkyl or C 1 -C 4 -alk Oxy-substituted -C y H 2y -(C 3 -C 8 -cycloalkylene)-C y H 2y -, wherein y is an integer of 1-6.
式IIb化合物的优选次组是这样的化合物，式中X为二价的-O-，-NH-，-S-或-(CH2)y-；Y10是-O-(CH2)y-或一直接的键，其中y为1-6的一个整数和其末端的CH2-基与在式(IIb)中的相邻X相连接；R100是H，C1-C12-烷基或C1-C12-烷氧基；R101为直链的低级烷基，低级链烯基或芳基低级烷基；R102与R101无关具有如R101相同的含义或为芳基，或R101和R102一起为-(CH2)m-，其中m为2-6的整数；R103和R104相互独立地为直链的或支链的低级烷基(它可以是以C1-C4-烷氧基取代的)，芳基低级烷基或低级链烯基；或R103和R104一起为-(CH2)z-Y11-(CH2)z-，其中Y11为一直接的键，-O-，-S-，或-NR1B-和R1B为H或低级烷基和z为2至4的一个整数；和R5为支链的C6-C10-亚烷基，亚苯基或以1至3个甲基取代的亚苯基，亚苄基或以1至3个甲基取代的亚苄基，亚环己基或以1至3个甲基取代的亚环己基，亚环己基-CH2-或以1至3个甲基取代的亚环己基-CH2-。A preferred subgroup of compounds of formula IIb are compounds wherein X is a divalent -O-, -NH-, -S- or -(CH 2 ) y -; Y 10 is -O-(CH 2 ) y - or a direct bond, wherein y is an integer of 1-6 and its terminal CH 2 -group is connected to the adjacent X in formula (IIb); R 100 is H, C 1 -C 12 -alk or C 1 -C 12 -alkoxy; R 101 is straight-chain lower alkyl, lower alkenyl or aryl lower alkyl; R 102 has the same meaning as R 101 irrespective of R 101 or is aryl , or R 101 and R 102 together are -(CH 2 ) m -, wherein m is an integer of 2-6; R 103 and R 104 are independently linear or branched lower alkyl (it can be in the form of C 1 -C 4 -alkoxy substituted), aryl lower alkyl or lower alkenyl; or R 103 and R 104 together are -(CH 2 ) z -Y 11 -(CH 2 ) z -, wherein Y 11 is a direct bond, -O-, -S-, or -NR 1B - and R 1B is H or lower alkyl and z is an integer from 2 to 4; and R 5 is branched C 6 - C 10 -Alkylene, phenylene or phenylene substituted with 1 to 3 methyl groups, benzylidene or benzylidene substituted with 1 to 3 methyl groups, cyclohexylene or substituted with 1 to 3 methyl groups Cyclohexylene substituted with methyl, cyclohexylene-CH 2 - or cyclohexylene-CH 2 - substituted with 1 to 3 methyl groups.
式IIb化合物特别优选的次组是这样的化合物，式中R101为甲基，烯丙基，甲苯甲酰甲基或苄基，R102为甲基，乙基，苄基或苯基或R101和R102一起是五亚甲基，R103和R104相互独立地为具有直至4C-原子的低级烷基或R103和R104一起为-CH2CH2-OCH2CH2-，和R5为支链的C6-C10-亚烷基，亚苯基或以1至3个甲基取代的亚苯基，亚苄基或以1至3个甲基取代的亚苄基，亚环己基或以1至3个甲基取代的亚环己基，亚环己基-CH2-或以1至3个甲基取代的亚环己基-CH2-。A particularly preferred subgroup of compounds of formula IIb are compounds in which R 101 is methyl, allyl, toluoylmethyl or benzyl, R 102 is methyl, ethyl, benzyl or phenyl or R 101 and R 102 together are pentamethylene, R 103 and R 104 independently of each other are lower alkyl having up to 4 C-atoms or R 103 and R 104 together are -CH 2 CH 2 -OCH 2 CH 2 -, and R5 is branched C 6 -C 10 -alkylene, phenylene or phenylene substituted with 1 to 3 methyl groups, benzylidene or benzylidene substituted with 1 to 3 methyl groups, Cyclohexyl or cyclohexylene substituted with 1 to 3 methyl groups, cyclohexylene -CH 2 - or cyclohexylene -CH 2 - substituted with 1 to 3 methyl groups.
基R4和R5尤其是涉及这样的基，它降低了OCN-基的反应活性，这主要是通过空间阻碍或电子对至少一相邻C-原子的影响实现的。此外R4和R5因此优选是不对称的基，例如在OCN-基的α-或特别是β-位上有支链的亚烷基，或至少在α-位上如定义取代的环烃基。The radicals R 4 and R 5 are in particular radicals which reduce the reactivity of the OCN radical mainly by steric hindrance or the influence of electrons on at least one adjacent C-atom. R4 and R5 are therefore preferably asymmetric radicals, for example alkylene groups branched in the α- or especially β-position of the OCN-group, or cyclohydrocarbyl groups substituted as defined at least in the α-position .
对可共聚合的乙烯基单体在本发明的范围内特别理解为一种单体，它含有乙烯基并在用于隐形眼镜的共聚物中已提到。因此对乙烯基不仅只理解为乙烯基化“-CH＝CH2”，而且通常也理解为每种具有碳-碳-双键的基。乙烯基单体中特别优选的组成部分“乙烯基”的含义由下面与式III化合物相联系的说明才会清楚。在本发明的意义上可共聚合的乙烯基单体例如已在EP-A-374,752，EP-A-417,235和EP-A-455,587中公开过。Within the scope of the present invention, a copolymerizable vinyl monomer is understood in particular to be a monomer which contains a vinyl group and which has been mentioned for the copolymers for contact lenses. Vinyl is therefore not only understood to mean the vinylation "-CH=CH 2 ", but generally also every radical having a carbon-carbon-double bond. The meaning of the "vinyl" moiety which is particularly preferred in vinyl monomers will become clear from the description below in connection with the compound of formula III. Copolymerizable vinyl monomers in the sense of the present invention are disclosed, for example, in EP-A-374,752, EP-A-417,235 and EP-A-455,587.
特别是这些单体，从这些单体出发以提供用于本发明嵌段共聚物，聚合物或隐形眼镜的式I组成部分A，式III化合物
它(用字母A表示)以部分式IV的形状嵌入式I嵌段共聚物中， It (denoted by the letter A) is embedded in the I block copolymer in the shape of part formula IV,
其中取代基W，X0，Y0和Z具有下面的含义：这些基的三个为氢和第4个取代基是在酰基，卤素，杂环基或芳基中间选择的，或这些基的2个为氢，第3个为低级烷基，和第4个取代基是选自酰基，卤素，杂环基或芳基，或这些基的2个为氢和其他的2个取代基共同形成一烃桥，它是未断开的或通过一个或二个杂原子断开的，或此2个其他的取代基为相互独立的酰基。式III单体或是亲水的乙烯基单体或是疏水的乙烯基单体。Wherein the substituents W, X 0 , Y 0 and Z have the following meanings: three of these groups are hydrogen and the fourth substituent is selected among acyl, halogen, heterocyclyl or aryl, or one of these groups 2 are hydrogen, the 3rd is lower alkyl, and the 4th substituent is selected from acyl, halogen, heterocyclyl or aryl, or 2 of these are hydrogen and other 2 substituents together A hydrocarbon bridge, which is unbroken or broken through one or two heteroatoms, or the two other substituents are acyl groups independently of each other. The monomer of formula III is either a hydrophilic vinyl monomer or a hydrophobic vinyl monomer.
芳基特别是具有6至15个碳原子的芳族烃基，如苯基或通过一个或多个(尤其直至3个)低级烷基，低级烷氧基，卤素，氨基或羟基类的基取代的苯基。例子是苯基或甲苯基。Aryl is especially an aromatic hydrocarbon group having 6 to 15 carbon atoms, such as phenyl or substituted by one or more (especially up to 3) lower alkyl, lower alkoxy, halogen, amino or hydroxy groups phenyl. Examples are phenyl or tolyl.
卤素特别是氯，溴或氟，但也可为碘。Halogen is especially chlorine, bromine or fluorine, but also iodine.
杂环基特别是具有1个或2个杂原子，如氧-或氮原子，尤其是具有1或2个氮原子的5元-或6元芳族的或饱和的环。其中也包括内酰胺。Heterocyclyl is in particular a 5- or 6-membered aromatic or saturated ring having 1 or 2 heteroatoms, such as oxygen or nitrogen atoms, especially 1 or 2 nitrogen atoms. These also include lactams.
烃桥(它是未断开的或通过1或2个杂原子断开的)特别是低级亚烷基或通过氧或氮断开的低级亚烷基。通过氮断开的低级亚烷基也可是取代的，例如通过低级烷基。例子是1，3-亚丙基，2-氮杂-1，3-亚丙基或N-甲基-2-氮杂-1，3-亚丙基。Hydrocarbon bridges, which are unbroken or broken through 1 or 2 heteroatoms, are in particular lower alkylene or lower alkylene broken through oxygen or nitrogen. Lower alkylene cleaved through nitrogen may also be substituted, for example through lower alkyl. Examples are 1,3-propylene, 2-aza-1,3-propylene or N-methyl-2-aza-1,3-propylene.
酰基为羧基，芳酰基，环烷酰基或烷酰基和尤其是为羧基，未取代的或取代的芳氧基羰基，未取代的或取代的环烷氧基羰基或未取代的或取代的烷氧基羰基。Acyl is carboxy, aroyl, cycloalkanoyl or alkanoyl and especially carboxy, unsubstituted or substituted aryloxycarbonyl, unsubstituted or substituted cycloalkoxycarbonyl or unsubstituted or substituted alkoxy base carbonyl.
芳酰基例如为苯甲酰基或通过1或多个(特别是直至3个)低级烷基，低级烷氧基，卤素或羟基类的基取代的苯甲酰基，但也可为苯磺酰基或苯氧磺酰基以及通过低级烷基，低级烷氧基，卤素或羟基取代的苯磺酰基或苯氧磺酰基。Aroyl is, for example, benzoyl or benzoyl substituted by 1 or more (in particular up to 3) lower alkyl, lower alkoxy, halogen or hydroxy-like radicals, but also benzenesulfonyl or benzene Oxysulfonyl and benzenesulfonyl or phenoxysulfonyl substituted by lower alkyl, lower alkoxy, halogen or hydroxy.
链烷酰基优选为低级链烷酰基和例如是乙酰基，丙酰基或丁酰基。Alkanoyl is preferably lower alkanoyl and is, for example, acetyl, propionyl or butyryl.
环烷酰基优选为具有直至8C-原子的环烷氧基羰基和例如为环己氧基羰基。Cycloalkanoyl is preferably cycloalkoxycarbonyl having up to 8 C-atoms and is, for example, cyclohexyloxycarbonyl.
未取代的烷氧基羰基优选是低级烷氧基羰基和例如为甲氧基羰基，乙氧基羰基，丙氧基羰基，丁氧基羰基，叔-丁氧基羰基，叔丁基甲氧羰基或2-乙基己氧基羰基。Unsubstituted alkoxycarbonyl is preferably lower alkoxycarbonyl and is for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, tert-butylmethoxycarbonyl or 2 - ethylhexyloxycarbonyl.
未取代的芳氧基羰基优选是苯氧基羰基。Unsubstituted aryloxycarbonyl is preferably phenoxycarbonyl.
取代的芳氧基羰基优选是通过1或多个(特别是直至3个)低级烷基，低级烷氧基，卤素或羟基类的基取代的苯氧基羰基。Substituted aryloxycarbonyl is preferably phenoxycarbonyl substituted by 1 or more (in particular up to 3) lower alkyl, lower alkoxy, halogen or hydroxy-like radicals.
取代的烷氧基羰基优选是通过疏水基，如卤素例如氟，硅氧烷基或亲水基，如羟基，氨基，单或二低级烷基氨基，异氰酸根合或通过低级烷二醇取代的。取代的烷氧基羰基，和还有取代的芳氧基羰基和取代的环烷氧基羰基的其他含义，通过下面的特别适宜的式III乙烯基单体的描述已隐含地给出。Substituted alkoxycarbonyl is preferably substituted by a hydrophobic group such as halogen such as fluorine, a siloxane group or a hydrophilic group such as hydroxy, amino, mono- or di-lower alkylamino, isocyanato or by a lower alkanediol of. The other meanings of substituted alkoxycarbonyl, and also substituted aryloxycarbonyl and substituted cycloalkoxycarbonyl, are given implicitly by the following description of particularly suitable vinyl monomers of the formula III.
本发明可应用的亲水乙烯基单体优选是式III的丙烯酸酯和甲基丙烯酸酯，式中W和Y0为氢，X0为氢或甲基和Z为-Z1-Z2基，式中Z1为-COO-，它经氧结合在Z2上，和Z2为一通过引起水溶的基如羧基，羟基或叔-氨基，例如每个低级烷基具有1至7碳原子的叔低级烷基氨基，具有2-100重复单元，优选具有2-40重复单元的聚环氧乙烷，或硫酸酯-，磷酸酯-，磺酸酯-或膦酸酯基一次或多次取代的具有1至10碳原子的烃基，例如相应取代的烷基，环烷基或苯基或这种基的结合，如苯基烷基或烷基环烷基；Hydrophilic vinyl monomers applicable in the present invention are preferably acrylates and methacrylates of formula III, wherein W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is a -Z 1 -Z 2 group , where Z1 is -COO-, which is bonded to Z2 via oxygen, and Z2 is a water-soluble group such as carboxyl, hydroxyl or tertiary-amino, for example, each lower alkyl group has 1 to 7 carbon atoms A tertiary lower alkylamino group having 2-100 repeating units, preferably polyethylene oxide having 2-40 repeating units, or a sulfate-, phosphate-, sulfonate- or phosphonate group one or more times Substituted hydrocarbyl radicals having 1 to 10 carbon atoms, such as correspondingly substituted alkyl, cycloalkyl or phenyl or combinations of such radicals, such as phenylalkyl or alkylcycloalkyl;
另外式III的丙烯酰胺和甲基丙烯酰胺，式中W和Y0为氢，X0为氢或甲基和Z为氨基羰基或二低级烷基氨基羰基；In addition, acrylamide and methacrylamide of formula III, wherein W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is aminocarbonyl or two lower alkylaminocarbonyl;
式III的丙烯酰胺和甲基丙烯酰胺，式中W和Y0为氢，X0为氢或甲基和Z为单取代的氨基羰基，它是通过一个如前面定义的基Z2或低级烷基取代的；Acrylamides and methacrylamides of formula III, wherein W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is a monosubstituted aminocarbonyl, which is obtained through a group Z as defined above or a lower alkane Substituted;
式III的马来酸酯和富马酸酯，式中W和X0(或W和Z)为氢，和Y0和Z(或X0和Y0)相互独立地为-Z1-Z2基，式中Z1和Z2定义如前面；Maleate and fumarate esters of formula III, wherein W and X 0 (or W and Z) are hydrogen, and Y 0 and Z (or X 0 and Y 0 ) are independently of each other -Z 1 -Z 2 bases, in the formula Z 1 and Z 2 are defined as before;
式III的丁烯酸酯，式中W和X0为氢，Y0为甲基和Z为-Z1-Z2基，式中Z1和Z2如前面定义；A crotonate ester of formula III, wherein W and X are hydrogen, Y is methyl and Z is a -Z 1 -Z 2 group, and Z 1 and Z 2 are as defined above in the formula;
式III的乙烯基醚，式中W，X0和Y0为氢和Z为-Z1-Z2基，式中Z1为氧和Z2如前面定义；Vinyl ethers of formula III, wherein W, X 0 and Y 0 are hydrogen and Z is a -Z 1 -Z 2 group, wherein Z 1 is oxygen and Z 2 is as defined above;
具有1或2个氮原子的乙烯基取代的5元或6元杂环以及式III的N-乙烯基内酰胺，如N-乙烯基-2-吡咯烷酮，式中W，X0和Y0为氢和Z为具有1或2个氮原子的5元或6元杂环的基，以及经氮结合的内酰胺基，例如2-吡咯烷酮的那种；Vinyl-substituted 5- or 6-membered heterocyclic rings with 1 or 2 nitrogen atoms and N-vinyllactams of formula III, such as N-vinyl-2-pyrrolidone, wherein W, X and Y are Hydrogen and Z are radicals of 5- or 6-membered heterocycles having 1 or 2 nitrogen atoms, and nitrogen-bonded lactam groups, such as those of 2-pyrrolidone;
式III的烯属不饱和的具有总共3至10碳原子的羧酸，如甲基丙烯酸，丁烯酸，富马酸或肉桂酸。Ethylenically unsaturated carboxylic acids of the formula III having a total of 3 to 10 carbon atoms, such as methacrylic acid, crotonic acid, fumaric acid or cinnamic acid.
优选的例如是通过羟基取代的C2-C4-烷基(甲基)丙烯酸酯，5至7节的N-乙烯基内酰胺，N，N-二-C1-C4-烷基(甲基)丙烯酰胺和烯属不饱和的具有总共3至5个碳原子的羧酸。Preferred are, for example, C 2 -C 4 -alkyl (meth)acrylates substituted by hydroxyl groups, N-vinyllactams of 5 to 7 segments, N,N-di-C 1 -C 4 -alkyl ( Meth)acrylamide and ethylenically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.
属于可应用的水溶性的单体有：2-羟基乙基，2-和3-羟基丙基，2，3-二羟基丙基，聚乙氧基乙基和聚乙氧基丙基丙烯酸酯和-甲基丙烯酸酯以及相应的丙烯酰胺类和甲基丙烯酰胺类，丙烯酰胺和甲基丙烯酰胺，N-甲基丙烯酰胺和-甲基丙烯酰胺，双丙酮-丙烯酰胺，2-羟基乙基丙烯酰胺，二甲基丙烯酰胺和-甲基丙烯酰胺以及羟甲基丙烯酰胺和-甲基丙烯酰胺，N，N-二甲基-和N，N-二乙基氨基乙基丙烯酸酯和-甲基丙烯酸酯以及相应的丙烯酰胺类和甲基丙烯酰胺类，N-叔-丁基氨基乙基甲基丙烯酸酯和-甲基丙烯酰胺，2-和4-乙烯基吡啶，4-和2-甲基-5-乙烯基吡啶，N-甲基-4-乙烯基哌啶，1-乙烯基-和2-甲基-1-乙烯基-咪唑，二甲基烯丙胺和甲基二烯丙胺以及对-，间-和邻-氨基苯乙烯，二甲氨基乙基乙烯基醚，N-乙烯基吡咯烷酮和2-吡咯烷基乙基(甲基丙烯酸)酯，丙烯酸和甲基丙烯酸，衣康酸，肉桂酸，丁烯酸，富马酸，马来酸和其羟基低级烷基单和-二酯，如2-羟基乙基-和二-(2-羟基)-乙基富马酸酯，-马来酸酯和-衣康酸酯，以及丁基富马酸3-羟基丙基酯和二-聚烷氧基烷基-富马酸酯，-马来酸酯和-衣康酸酯，马来酸酐，N-甲基马来酰亚胺，丙烯酸钠和甲基丙烯酸钠，2-甲基丙烯酰氧基乙基磺酸，2-丙烯酰胺基-2-甲基丙烷磺酸，甲基丙烯酸2-磷乙基酯，乙烯基磺酸，苯基乙烯基磺酸酯，乙烯基磺酸钠，对-苯乙烯磺酸，对-苯乙烯磺酸钠和烯丙基磺酸，N-乙烯基吡咯烷酮，N-乙烯基吡啶酮，N-乙烯基己内酰胺，另外四元化的阳离子单体的衍生物，它是用选出的烷基化剂如卤化烃例如甲基碘，苄基氯或十六烷氯，环氧化物如缩水甘油，表氯醇或环氧乙烷，丙烯酸，二甲基硫酸酯，甲基硫酸酯和丙烷磺内酯通过四元化得到的。Among the applicable water-soluble monomers are: 2-hydroxyethyl, 2- and 3-hydroxypropyl, 2,3-dihydroxypropyl, polyethoxyethyl and polyethoxypropyl acrylate and -methacrylates and corresponding acrylamides and methacrylamides, acrylamide and methacrylamide, N-methacrylamide and -methacrylamide, diacetone-acrylamide, 2-hydroxyethyl methacrylamide, dimethylacrylamide and -methacrylamide and methylolacrylamide and -methacrylamide, N,N-dimethyl- and N,N-diethylaminoethylacrylate and -methacrylates and corresponding acrylamides and methacrylamides, N-tert-butylaminoethyl methacrylate and -methacrylamide, 2- and 4-vinylpyridine, 4- and 2-methyl-5-vinylpyridine, N-methyl-4-vinylpiperidine, 1-vinyl- and 2-methyl-1-vinyl-imidazole, dimethylallylamine and methyldi Allylamine and p-, m- and o-aminostyrene, dimethylaminoethyl vinyl ether, N-vinylpyrrolidone and 2-pyrrolidinylethyl (methacrylate), acrylic and methacrylic acid, Itaconic acid, cinnamic acid, crotonic acid, fumaric acid, maleic acid and their hydroxy lower alkyl mono- and -diesters, such as 2-hydroxyethyl- and di-(2-hydroxy)-ethylfumaric acid esters, -maleate and -itaconate, and 3-hydroxypropyl butyl fumarate and di-polyalkoxyalkyl-fumarate, -maleate and -itaconate Conic acid esters, maleic anhydride, N-methylmaleimide, sodium acrylate and methacrylate, 2-methacryloyloxyethylsulfonic acid, 2-acrylamido-2-methylpropane Sulfonic acid, 2-phosphoethyl methacrylate, vinylsulfonic acid, phenylvinylsulfonate, sodium vinylsulfonate, p-styrenesulfonic acid, sodium p-styrenesulfonate and allyl Derivatives of sulfonic acids, N-vinylpyrrolidone, N-vinylpyridone, N-vinylcaprolactam, other quaternized cationic monomers, which are obtained with selected alkylating agents such as halogenated hydrocarbons such as methyl Iodine, benzyl chloride or hexadecyl chloride, epoxides such as glycidol, epichlorohydrin or ethylene oxide, acrylic acid, dimethylsulfate, methylsulfate and propane sultone obtained by quaternization .
较完整的与此发明有关的可用的水溶性的单体表出现在：R.H.Yocum和E.B.Nyquist，官能的单体[Funktionelle Monomere]，卷1，S.424-440(M.Dekker，N.Y.1973).A more complete list of available water-soluble monomers relevant to this invention appears in: R.H.Yocum and E.B.Nyquist, Functional Monomers [Funktionelle Monomere], Vol. 1, S.424-440 (M.Dekker, N.Y. 1973) .
优选的亲水的乙烯基单体是甲基丙烯酸2-羟基乙基酯，甲基丙烯酸3-羟基丙基酯，N-乙烯基-2-吡咯烷酮，聚甲基丙烯酸乙二醇酯，尤其是具有分子量约为400的乙二醇部分，N，N-二甲基丙烯酰胺以及丙烯酸和甲基丙烯酸。Preferred hydrophilic vinyl monomers are 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, N-vinyl-2-pyrrolidone, poly(ethylene glycol methacrylate), especially Has an ethylene glycol moiety with a molecular weight of about 400, N,N-dimethylacrylamide as well as acrylic and methacrylic acid.
作为疏水的乙烯基单体(必要时按照本发明使用它们)例如考虑：Examples of hydrophobic vinyl monomers (which are used according to the invention if appropriate) include, for example:
式III丙烯酸酯和甲基丙烯酸酯，式中W和Y0为氢，X0为氢或甲基和Z为-Z1-Z3基，式中Z1为-COO-，它经氧结合在Z3上，和Z3是一直链的或支链的脂族的，环脂族的或芳族的具有1至21碳原子的基，例如相应取代的烷基-，环烷基-或苯基或这些基的结合，如苯基烷基或烷基环烷基，它们可含有醚键或硫醚键，亚砜或砜基或羰基；或Z3是一杂环基，它含有氧-，硫-或氮原子和5或6，或若它是双环的，直至10个环原子，或一具有2至50个重复的烷氧基单元的聚环氧丙烷-或聚-正-环氧丁烷基，或Z3是一具有1-12个碳原子的烷基，它含有卤素原子，特别是氟原子，或Z3是一具有1至6Si-原子的硅氧烷基；Acrylates and methacrylates of formula III, where W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is -Z 1 -Z 3 groups, where Z 1 is -COO-, which is bonded via oxygen On Z3 , and Z3 is a linear or branched aliphatic, cycloaliphatic or aromatic group with 1 to 21 carbon atoms, such as a correspondingly substituted alkyl-, cycloalkyl- or Phenyl or the combination of these groups, such as phenylalkyl or alkylcycloalkyl, they may contain ether bond or thioether bond, sulfoxide or sulfone group or carbonyl; or Z3 is a heterocyclic group, which contains oxygen -, sulfur- or nitrogen atoms and 5 or 6, or if it is bicyclic, up to 10 ring atoms, or a polypropylene oxide- or poly-n-ring with 2 to 50 repeating alkoxy units Oxybutylene, or Z 3 is an alkyl group with 1-12 carbon atoms, which contains a halogen atom, especially a fluorine atom, or Z 3 is a siloxane group with 1 to 6 Si-atoms;
式III丙烯酰胺和甲基丙烯酰胺，式中W和Y0为氢，X0为氢或甲基和Z为单取代的氨基羰基，它是通过一如前定义的基Z3取代的；Formula III acrylamide and methacrylamide, wherein W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is a monosubstituted aminocarbonyl, which is substituted by a group Z as defined above;
式III马来酸酯和富马酸酯，式中W和X0(或W和Z)为氢，和Y0和Z(或X0和Y0)相互独立地为-Z1-Z3基，式中Z1和Z3如前面定义；Formula III maleate and fumarate, wherein W and X 0 (or W and Z) are hydrogen, and Y 0 and Z (or X 0 and Y 0 ) are independently -Z 1 -Z 3 Base, Z 1 and Z 3 are as defined above in the formula;
式III衣康酸酯，式中W和Y0为氢，X0为-Z1-Z3基，式中Z1和Z3如前面定义的和Z为-CH2-Z1-Z3基，式中Z1和Z3如前面定义的；Formula III itaconate, wherein W and Y 0 are hydrogen, X 0 is a -Z 1 -Z 3 group, wherein Z 1 and Z 3 are as defined above and Z is -CH 2 -Z 1 -Z 3 Base, in the formula Z 1 and Z 3 as previously defined;
式III丁烯酸酯，式中W和X0为氢，Y0为甲基和Z为-Z1-Z3基，式中Z1和Z3如前面定义；Formula III crotonate, wherein W and X 0 are hydrogen, Y 0 is a methyl group and Z is a -Z 1 -Z 3 base, and Z 1 and Z 3 are as defined above in the formula;
式III乙烯基酯，式中W，Y0和X0为氢和Z为-Z1-Z3基，式中Z1为-COO-，它经碳结合在Z3上，和Z3如前面定义；Vinyl esters of formula III, wherein W, Y 0 and X 0 are hydrogen and Z is a -Z 1 -Z 3 group, wherein Z 1 is -COO-, which is bonded to Z 3 via carbon, and Z 3 is as previously defined;
式III乙烯基醚，式中W，X0和Y0为氢和Z为-Z1-Z3基，式中Z1为氧和Z3如前面定义；Vinyl ether of formula III, wherein W, X 0 and Y 0 are hydrogen and Z is a -Z 1 -Z 3 base, wherein Z 1 is oxygen and Z 3 is as defined above;
特别优选是烯属不饱和的具有3至5碳原子的羰酸的C1-C4-烷基酯或C5-C7-环烷基酯。Particular preference is given to C 1 -C 4 -alkyl or C 5 -C 7 -cycloalkyl esters of ethylenically unsaturated carboxylic acids having 3 to 5 carbon atoms.
适宜的疏水单体的例子是甲基，乙基，丙基，异丙基，丁基，异丁基，叔-丁基，乙氧基乙基，甲氧基乙基，苄基，苯基，环己基，三甲基环己基，异冰片基，二环戊二烯基，降冰片基甲基，环十二烷基，1，1，3，3-四甲基丁基，n-丁基，n-辛基，2-乙基己基，癸烷基，十二烷基，十三烷基，十八烷基，缩水甘油基，乙基硫乙基，呋喃基，三-，四-和五-硅氧烷基丙基-丙烯酸酯和-甲基丙烯酸酯，以及相应的酰胺；N(1，1-二甲基-3-氧代丁基)-丙烯酰胺；单-和二甲基-富马酸酯，-马来酸酯和-衣康酸酯；二乙基-富马酸酯；异丙基-和二异丙基-富马酸酯和-衣康酸酯；单-和二苯基-和甲基苯基-富马酸酯和-衣康酸酯；甲基-和乙基丁烯酸酯；甲基乙烯基醚和甲氧基乙基乙烯基醚，乙酸乙烯基酯，丙酸乙烯基酯，苯甲酸乙烯基酯，丙烯腈，二氯乙烯，苯乙烯，α-甲基苯乙烯和叔-丁基苯乙烯。Examples of suitable hydrophobic monomers are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, ethoxyethyl, methoxyethyl, benzyl, phenyl , cyclohexyl, trimethylcyclohexyl, isobornyl, dicyclopentadienyl, norbornylmethyl, cyclododecyl, 1,1,3,3-tetramethylbutyl, n-butyl base, n-octyl, 2-ethylhexyl, decanyl, dodecyl, tridecyl, octadecyl, glycidyl, ethylthioethyl, furyl, tri-, tetra- and penta-siloxanylpropyl-acrylates and -methacrylates, and the corresponding amides; N(1,1-dimethyl-3-oxobutyl)-acrylamide; mono- and dimethyl diethyl-fumarate, -maleate and -itaconate; diethyl-fumarate; isopropyl- and diisopropyl-fumarate and -itaconate; - and diphenyl- and methylphenyl-fumarate and -itaconate; methyl- and ethyl crotonate; methyl vinyl ether and methoxyethyl vinyl ether, acetic acid Vinyl esters, vinyl propionate, vinyl benzoate, acrylonitrile, vinylidene chloride, styrene, alpha-methylstyrene and tert-butylstyrene.
优选的疏水乙烯基单体是甲基丙烯酸甲基酯，甲基丙烯酸n-丁基酯，甲基丙烯酸异丙基酯，甲基丙烯酸异丁基酯，甲基丙烯酸环己基酯或它们的混合物。Preferred hydrophobic vinyl monomers are methyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate or mixtures thereof .
在前面提到的乙烯基单体中与本发明有关的二种特殊类型的疏水的乙烯基单体特别值得述及，即硅氧烷单乙烯基组分和含氟的乙烯基化合物。Of the aforementioned vinyl monomers, two particular classes of hydrophobic vinyl monomers which are relevant to the present invention deserve particular mention, namely silicone monovinyl components and fluorine-containing vinyl compounds.
特别优选的硅氧烷单乙烯基组分是式III化合物，式中W和Y0为氢，X0为氢或甲基和Z为-Z1-Z4基，式中Z1为-COO-，它经氧结合在Z4上和式中Z4是一次或多次，例如3至9次，通过三低级烷基甲硅烷氧基取代的甲硅烷基-低级烷基。对甲硅烷基-低级烷基因此理解为一种通过一或多个硅原子取代的低级烷基，其在硅原子上的自由价特别是通过三低级烷基甲硅烷氧基饱和的。特别要强调的单一化合物例如是甲基丙烯酸三(三甲基甲硅烷氧基)甲硅烷基丙基酯和甲基丙烯酸三(三(三甲基甲硅烷氧基)甲硅烷氧基)甲硅烷基丙基酯。Particularly preferred siloxane monovinyl components are compounds of formula III, where W and Y0 are hydrogen, X0 is hydrogen or methyl and Z is a -Z1 - Z4 group, where Z1 is -COO -, which is bonded to Z4 via oxygen and wherein Z4 is silyl-lower alkyl substituted one or more times, for example 3 to 9 times, by tri-lower alkylsilyloxy. A p-silyl-lower alkyl group is thus understood to be a lower alkyl group substituted by one or more silicon atoms, the free valences of which are saturated on the silicon atoms, in particular by tri-lower alkylsiloxy groups. Individual compounds to be particularly emphasized are, for example, tris(trimethylsiloxy)silylpropyl methacrylate and tris(tris(trimethylsiloxy)siloxy)silyl methacrylate Propyl ester.
特别优选的含氟的乙烯基化合物是式III化合物，式中W和Y0为氢，X0为氢或甲基和Z为-Z1-Z5基，式中Z1为-COO-，它经氧结合在Z5上和式中Z5是通过氟取代的烷基，尤其是低级烷基。这里专门的例子是甲基丙烯酸2，2，2-三氟乙基酯，甲基丙烯酸2，2，3，3-四氟丙基酯，甲基丙烯酸2，2，3，3，4，4，5，5-八氟戊基酯和甲基丙烯酸六氟异丙基酯。Particularly preferred fluorine-containing vinyl compounds are compounds of formula III, wherein W and Y 0 are hydrogen, X 0 is hydrogen or methyl and Z is a -Z 1 -Z 5 group, wherein Z 1 is -COO-, It is bonded to Z5 via oxygen and wherein Z5 is alkyl, especially lower alkyl, substituted by fluorine. Specific examples here are 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4 methacrylate, 4,5,5-Octafluoropentyl ester and hexafluoroisopropyl methacrylate.
如已提到的，式I的共聚物是特别优选的，其中涉及三嵌段共聚物，梳型聚合物或星型聚合物。对所有这三种式I共聚物类型，但尤其是对三嵌段共聚物，都适用下述这样是特别优选的，式中Macro为聚硅氧烷的基或氟化的聚醚的基和A部分是来自具有一反应基的亲水的乙烯基单体。反应基特别涉及羟基或异氰酸根合。具有这种基的乙烯基单体的例子是(甲基)丙烯酸羟基-低级烷基酯或(甲基)丙烯酸异氰酸根合-低级烷基酯，如特别是甲基丙烯酸羟基乙基酯或甲基丙烯酸异氰酸根合乙基酯。As already mentioned, copolymers of the formula I are particularly preferred, these being triblock copolymers, comb polymers or star polymers. For all three types of copolymers of the formula I, but especially for triblock copolymers, it is particularly preferred that Macro is a radical of a polysiloxane or a radical of a fluorinated polyether and Part A is derived from a hydrophilic vinyl monomer having a reactive group. The reactive groups are in particular hydroxyl or isocyanato. Examples of vinyl monomers having such groups are hydroxy-lower alkyl (meth)acrylates or isocyanato-lower alkyl (meth)acrylates, such as especially hydroxyethyl methacrylate or Isocyanatoethyl methacrylate.
另外优选的是式I共聚物，尤其是三嵌段共聚物，式中Macro为聚硅氧烷的基或氟化的聚醚的基和A部分是来自没有反应基的亲水的乙烯基单体。这样的乙烯基单体特别是乙烯基丙酰胺，主要是N-乙烯基吡咯烷酮。另外式I共聚物，特别是嵌段共聚物，也是优选的，式中Macro为亲水大基体的基，如前面定义的，和部分A是来自疏水的乙烯基单体。Also preferred are copolymers of formula I, especially triblock copolymers, in which Macro is a group of polysiloxane or a group of fluorinated polyether and part A is derived from a hydrophilic vinyl unit without reactive groups. body. Such vinyl monomers are in particular vinylpropionamides, mainly N-vinylpyrrolidone. Also preferred are copolymers of formula I, especially block copolymers, wherein Macro is the radical of the hydrophilic macromatrix, as previously defined, and moiety A is derived from a hydrophobic vinyl monomer.
如已提到的，本发明的聚合物优选是由式C化合物和乙烯基单体在交联剂存在时制备的。As already mentioned, the polymers of the invention are preferably prepared from compounds of formula C and vinyl monomers in the presence of crosslinkers.
适合的交联剂特别是低烯烃的，尤其是二烯烃的单体，例如烯丙基丙烯酸酯和-甲基丙烯酸酯，乙二醇-，二乙二醇-，三乙二醇-，四乙二醇-和一般的聚环氧乙烷二元醇二丙烯酸酯和二(甲基丙烯酸)酯，1，4-丁二醇-和聚-正-环氧丁烷二元醇二丙烯酸酯和-二(甲基丙烯酸)酯，丙二醇-和聚环氧丙烷二元醇二丙烯酸酯和-二(甲基丙烯酸)酯，硫二乙二醇二丙烯酸酯和-二(甲基丙烯酸)酯，二-(2-羟基乙基)-砜二丙烯酸酯和-二(甲基丙烯酸)酯，新戊二醇二丙烯酸酯和-二(甲基丙烯酸)酯，三羟甲基丙烷-三-和-四丙烯酸酯，季戊四醇-三-和-四-丙烯酸酯，二乙烯基苯，二乙烯基醚，二乙烯基砜，二硅氧烷基-双-3-羟基丙基-二丙烯酸酯或-甲基丙烯酸酯和相关的化合物。乙二醇二(甲基丙烯酸)酯是优选的。Suitable crosslinking agents are especially low olefinic, especially diolefinic monomers, such as allyl acrylate and -methacrylate, ethylene glycol-, diethylene glycol-, triethylene glycol-, tetra Ethylene glycol- and common polyethylene oxide diol diacrylates and di(methacrylate) esters, 1,4-butanediol- and poly-n-butylene oxide diol diacrylates and-di(methacrylate)ester, propylene glycol-and-polypropylene oxide diol diacrylate and-di(methacrylate)ester, thiodiethylene glycol diacrylate and-di(methacrylate)ester , Di-(2-hydroxyethyl)-sulfone diacrylate and -di(methacrylate) ester, neopentyl glycol diacrylate and -di(methacrylate) ester, trimethylolpropane-tri- and-tetraacrylate, pentaerythritol-tri-and-tetra-acrylate, divinylbenzene, divinyl ether, divinylsulfone, disiloxane-bis-3-hydroxypropyl-diacrylate or - Methacrylates and related compounds. Ethylene glycol di(methacrylate) is preferred.
作为交联剂也考虑低乙烯基大基体，例如二乙烯基大基体，如在US-A-4,136,250中所描述的。另外作为与本发明有关的交联剂低乙烯基硅氧烷化合物也是适合的，例如双(甲基)-丙烯酰氧基-低级烷基-硅氧烷(直至10个硅原子)。这里的例子是3，5-双(3-甲基丙烯酰氧基丙基)-3，5-双(三甲基甲硅烷氧基)-1，1，1，7，7，7-六甲基四硅氧烷和1，3-二(甲基丙烯酰氧基)丙基-四甲基二硅氧烷。Also contemplated as crosslinkers are low vinyl macromatrixes, for example divinyl macromatrixes, as described in US-A-4,136,250. Also suitable as crosslinkers in connection with the invention are low vinyl siloxane compounds, such as bis(meth)-acryloyloxy-lower alkyl-siloxanes (up to 10 silicon atoms). An example here is 3,5-bis(3-methacryloxypropyl)-3,5-bis(trimethylsilyloxy)-1,1,1,7,7,7-hexa Methyltetrasiloxane and 1,3-bis(methacryloxy)propyl-tetramethyldisiloxane.
制备本发明的共聚物，聚合物和接枝共聚物时使用的原料，例如式A，B，III的这种和交联剂是本身已知的和/或这里已描述过。The starting materials used in the preparation of the copolymers, polymers and graft copolymers according to the invention, for example those of the formulas A, B, III and crosslinkers are known per se and/or have been described here.
式II化合物可以本身已知的方法通过二异氰酸酯与相应的H-酸的光引发剂的反应制造。即使在光引发剂中同时出现二种不同的反应的H-酸基时，例如二个OH基，得到的化合物也是高产率的和高纯度的。特别有利的是，使用具有不同反应性的异氰酸酯基的二异氰酸酯，因为就此可以进一步抑制异构体和二加成物的生成。不同的反应性例如可如前面已描述的通过空间的障碍引起。不同的反应性也可通过在二异氰酸酯中的异氰酸酯基得到，例如用羧酸或羟基胺，式IIa化合物由EP-A-632329是已知的。The compounds of the formula II can be produced in a manner known per se by reaction of diisocyanates with the corresponding photoinitiators of H-acids. Even when two different reactive H-acid groups are simultaneously present in the photoinitiator, eg two OH groups, the resulting compound is high yield and high purity. It is particularly advantageous to use diisocyanates having isocyanate groups of different reactivity, since the formation of isomers and di-adducts can be further suppressed in this way. Different reactivity can be brought about, for example, by spatial barriers as already described above. Different reactivities can also be obtained via isocyanate groups in diisocyanates, for example with carboxylic acids or hydroxylamines, compounds of the formula IIa are known from EP-A-632329.
式(IIb)化合物可通过下述方法制备，使式IIc化合物式中X，Y，R，R1，R2，R3和R4具有前面已陈述的含义，优选在一惰性有机溶剂中与式IId二异氰酸酯或必要时这样单封闭的二异氰酸酯反应The compound of formula (IIb) can be prepared by the following method, making the compound of formula IIc In the formula, X, Y, R, R 1 , R 2 , R 3 and R 4 have the previously stated meanings, preferably reacted in an inert organic solvent with a diisocyanate of the formula IId or, if necessary, such a monoblocked diisocyanate
OCN-R5-NCO (IId)式中R5具有前面已陈述的含义，In the OCN-R 5 -NCO (IId) formula, R 5 has the previously stated meaning,
封闭剂是由《尿烷化学》已知的。例如它可涉及酚类(甲酚，二甲苯酚)，内酰胺(ε-己内酰胺)，肟(丙酮肟，二苯甲酮肟)，H-活化的亚甲基化合物(丙二酸二乙基酯，乙酰乙酸乙基酯)，吡唑或苯三唑。封闭剂例如是由Z.W.Wicks，Jr.in Progress inOrganic coatings，9(1981)，Seiten 3-28描述过。Sealants are known from Urethane Chemistry. For example it can involve phenols (cresol, xylenol), lactams (ε-caprolactam), oximes (acetone oxime, benzophenone oxime), H-activated methylene compounds (diethylmalonate ester, ethyl acetoacetate), pyrazole or benzotriazole. Sealing agents are described, for example, by Z.W. Wicks, Jr. in Progress in Organic coatings, 9 (1981), Seiten 3-28.
式IIc类型的离析物是已知的并例如描述在EP-A-284,561，EP-A-117,233或EP-A-088,050。Educts of the type IIc type are known and described, for example, in EP-A-284,561, EP-A-117,233 or EP-A-088,050.
适宜的惰性溶剂是质子惰性的非极性的或极性的溶剂例如烃类(石油醚，甲基环己烷，苯，甲苯，二甲苯)，卤化烃类(氯仿，二氯甲烷，三氯乙烷，四氯乙烷，氯苯)，醚(二乙基醚，二丁基醚，乙二醇二甲基醚，二乙二醇二甲基醚，四氢呋喃(THF)，二噁烷)，酮类(丙酮，二丁基酮，甲基-异丁基酮)，羧酸酯和内酯(乙酸乙基酯，丁内酯，戊内酯)，烷基化的羧酸酰胺(N，N-二甲基乙酰胺(DMA)或N，N-二甲基甲酰胺(DMF)，N-甲基-2-吡咯烷酮(NMP))，腈(乙腈)，砜和亚砜(二甲基亚砜(DMSO)，四亚甲基砜)。优选使用极性溶剂。Suitable inert solvents are aprotic nonpolar or polar solvents such as hydrocarbons (petroleum ether, methylcyclohexane, benzene, toluene, xylene), halogenated hydrocarbons (chloroform, dichloromethane, trichloro Ethane, tetrachloroethane, chlorobenzene), ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran (THF), dioxane) , ketones (acetone, dibutyl ketone, methyl-isobutyl ketone), carboxylic acid esters and lactones (ethyl acetate, butyrolactone, valerolactone), alkylated carboxylic acid amides (N , N-dimethylacetamide (DMA) or N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP)), nitrile (acetonitrile), sulfone and sulfoxide (dimethyl sulfoxide (DMSO), tetramethylene sulfone). Preference is given to using polar solvents.
有利的是以等摩尔的数量投入反应物。反应温度例如可为0至200℃。在应用催化剂时温度有利地可处于-20°至60℃的范围并优选-10至50℃的范围。适合的催化剂例如是金属盐如羧酸的碱金属盐，叔胺，例如(C1-C6-烷基)3N(三乙基胺，三-n-丁基胺)，N-甲基吡咯烷，N-甲基吗啉，N，N-二甲基哌啶，吡啶和1，4-二氮杂-双环辛烷。锡化合物证实特别有效，特别是羧酸的烷基锡盐，例如二月桂酸二丁基锡或例如二辛酸锡。The reactants are advantageously charged in equimolar amounts. The reaction temperature may be, for example, 0 to 200°C. The temperature when using the catalyst can advantageously be in the range of -20° to 60°C and preferably in the range of -10 to 50°C. Suitable catalysts are, for example, metal salts such as alkali metal salts of carboxylic acids, tertiary amines, for example (C 1 -C 6 -alkyl) 3 N (triethylamine, tri-n-butylamine), N-methyl Pyrrolidine, N-methylmorpholine, N,N-dimethylpiperidine, pyridine and 1,4-diaza-bicyclooctane. Tin compounds have proven particularly effective, in particular alkyltin salts of carboxylic acids, such as dibutyltin dilaurate or, for example, tin dioctoate.
如果在式IIc化合物中存在自由的NH-基，则这种基在与二异氰酸酯反应期间用适宜保护基首先保护起来并此后通过保护基的分解又释放出来。适宜的保护基对专业技术人员来说是已公知的。代表性的例子例如可由T.W.Greene，“有机合成中的保护基(Protective Groups in Organic Synthesis)” ，WileyInterscience，1981，获得。If a free NH group is present in the compound of the formula IIc, this group is first protected with a suitable protecting group during the reaction with the diisocyanate and is then released again by decomposition of the protecting group. Suitable protecting groups are known to the skilled person. Representative examples are available eg from T.W. Greene, "Protective Groups in Organic Synthesis", Wiley Interscience, 1981.
制备的化合物的分离和纯化是按已知方法进行的例如提取，结晶，重结晶或色谱的纯化方法。得到的化合物是高产率的和高纯度的。非优化方法的产率可超过理论的85％。Isolation and purification of the prepared compounds are performed according to known methods such as extraction, crystallization, recrystallization or chromatographic purification methods. The compounds obtained are high yield and high purity. The yield of the non-optimized method can exceed 85% of theory.
式A大基体与式B光引发剂的反应可简单地和以在《尿烷化学》中本身已知的方法进行。The reaction of the macromatrix of the formula A with the photoinitiator of the formula B can be carried out simply and in a manner known per se from "Urethane Chemistry".
反应产物(由式A大基体和式B光引发剂构成)与乙烯基单体(它作为组成部分“A”嵌入共聚物中)的反应可同样地以本身已知的方式进行。因此反应产物(由式A大基体和式B光引发剂构成)与乙烯基单体(它作为组成部分“A”嵌入共聚物中)在室温或在最大直至必要时使用的溶剂的沸点温度在不存在或存在适宜的溶剂时可以共聚。适宜的溶剂是例如烃，如己烷，苯或甲苯，或醚，如二乙基醚或四氢呋喃，或醇，如乙醇或异丙醇，或酰胺，如N-甲基吡咯烷酮，或二甲基亚砜，或多种这些溶剂的混合物。纯化以本身已知的方式实现。对交联反应成本发明的聚合物和接枝聚合物原则上可使用相同的条件。The reaction of the reaction product (consisting of a macromatrix of the formula A and a photoinitiator of the formula B) with vinyl monomers, which are embedded as constituent "A" in the copolymer, can likewise be carried out in a manner known per se. Thus the reaction product (consisting of the macromatrix of formula A and the photoinitiator of formula B) with the vinyl monomer (which is embedded as part "A" in the copolymer) at room temperature or at the boiling point of the solvent used up to the maximum if necessary Copolymerization is possible in the absence or presence of a suitable solvent. Suitable solvents are, for example, hydrocarbons, such as hexane, benzene or toluene, or ethers, such as diethyl ether or tetrahydrofuran, or alcohols, such as ethanol or isopropanol, or amides, such as N-methylpyrrolidone, or dimethyl sulfoxides, or mixtures of these solvents. Purification is achieved in a manner known per se. The same conditions can in principle be used for the crosslinking reaction of the polymers according to the invention and of the grafted polymers.
提到的接枝聚合的适宜烯烃例如是丙烯酰胺，N，N-二甲基丙烯酰胺，甲基丙烯酰胺，甲基丙烯酸羟基乙基酯，甲基丙烯酸甘油基酯，低环氧乙烷单和双丙烯酸酯，乙二醇二(甲基丙烯酸)酯，亚甲基双丙烯酰胺，乙烯基己内酰胺，丙烯酸，甲基丙烯酸，富马酸单乙烯基酯，乙烯基三氟乙酸酯和亚乙烯基碳酸酯，其中必要时可接着水解活性的酯。Suitable olefins mentioned for graft polymerization are for example acrylamide, N,N-dimethylacrylamide, methacrylamide, hydroxyethyl methacrylate, glyceryl methacrylate, low ethylene oxide mono and diacrylate, ethylene glycol di(methacrylate), methylene bisacrylamide, vinyl caprolactam, acrylic acid, methacrylic acid, monovinyl fumarate, vinyl trifluoroacetate and ethylene Vinyl carbonates, where necessary followed by hydrolysis-active esters.
在一定的情况使用二种或多种光引发剂的混合物是有利的。当然也可使用已知光引发剂的混合物，例如具有二苯酮，乙酰苯衍生物，苯偶姻醚或苯偶酰缩酮的混合物。In certain cases it may be advantageous to use a mixture of two or more photoinitiators. It is of course also possible to use mixtures of known photoinitiators, for example mixtures with benzophenones, acetophenone derivatives, benzoin ethers or benzil ketals.
为加速光聚合可添加胺，例如三乙醇胺，N-甲基-二乙醇胺，p-二甲氨基苯甲酸乙酯或米蚩酮。胺的作用通过加入芳族的二苯酮类型的酮可以强化。Amines such as triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone can be added to accelerate the photopolymerization. The action of amines can be enhanced by adding aromatic benzophenone-type ketones.
另外加速光聚合可通过加入光敏剂实现，它推延或加宽光谱的灵敏度。特别是芳族的羰基化合物例如二苯酮-，噻吨酮-，蒽醌-和3-酰基苯并邻吡喃酮衍生物以及3-(芳酰基亚甲基)-噻唑啉是这种情况。Additionally accelerated photopolymerization can be achieved by adding photosensitizers, which prolong or broaden the sensitivity of the spectrum. This is especially the case for aromatic carbonyl compounds such as benzophenone-, thioxanthone-, anthraquinone- and 3-acylbenzopyrone derivatives as well as 3-(aroylmethylene)-thiazoline .
光引发剂的有效性可通过加入带有有机氟基的钛茂衍生物使之提高，如在EP-A-122,223和EP-A-186,626已描述的，例如数量为1-20％。这样的钛茂的例子是双(甲基环戊二烯基)-双(2，3，6-三氟苯基)-钛，双(环戊二烯基)-双-(4-二丁基氨基-2，3，5，6-四氟苯基)-钛，双(甲基环戊二烯基)-2-(三氟甲基)苯基-异氰酸钛，双(环戊二烯基)-2-(三氟甲基)苯基-三氟乙酸钛或双(甲基环戊二烯基)-双(4-癸氧基-2，3，5，6-四氟苯基)-钛。对这些混合物液体的α-氨基酮最适合。The effectiveness of the photoinitiator can be increased by adding titanocene derivatives bearing organofluorine groups, as already described in EP-A-122,223 and EP-A-186,626, for example in amounts of 1-20%. Examples of such titanocenes are bis(methylcyclopentadienyl)-bis(2,3,6-trifluorophenyl)-titanium, bis(cyclopentadienyl)-bis-(4-dibutyl Amino-2,3,5,6-tetrafluorophenyl)-titanium, bis(methylcyclopentadienyl)-2-(trifluoromethyl)phenyl-titanium isocyanate, bis(cyclopentadienyl) Dienyl)-2-(trifluoromethyl)phenyl-titanium trifluoroacetate or bis(methylcyclopentadienyl)-bis(4-decyloxy-2,3,5,6-tetrafluoro phenyl)-titanium. Alpha-amino ketones are most suitable for these mixture liquids.
由本发明链段共聚物和特别是由本发明聚合物可以本身已知的方法制备模制体，特别是隐形眼镜。为此例如在圆柱形模具内聚合本发明的聚合物，并在脱模后将得到的棒切成片或块。它们可进一步机械加工，尤其是通过旋转方法。此外本发明的模制体和镜片也可按其他本身为已知的方法如在静止的模具中浇注，旋转浇注，压制，深冲，热成形，旋转或激光加工制造。这些方法步骤本身是已知的并因此对普通技术人员来说无需详细说明。Molded bodies, in particular contact lenses, can be produced from the segmented copolymers of the invention and in particular from the polymers of the invention in a manner known per se. For this purpose, the polymers according to the invention are polymerized, for example, in cylindrical molds and, after demoulding, the rods obtained are cut into sheets or pieces. They can be further machined, especially by the rotary method. Furthermore, the molded bodies and lenses according to the invention can also be produced by other methods known per se, such as casting in stationary molds, rotocasting, pressing, deep drawing, thermoforming, rotary or laser processing. These method steps are known per se and therefore do not require a detailed explanation for the person skilled in the art.
若生产在开放的模具中进行时，优选在惰性气氛下制作。公知氧抑制聚合并导致聚合时间延长。若使用封闭模具形成聚合物，则模具有利地由惰性的具有低透氧性的和不粘结性能的物料构成。适宜的模料例子是聚四氟乙烯，如特氟隆，硅橡胶，聚乙烯，聚丙烯和聚酯如Mylar。在使用脱模剂时玻璃模具和金属模具也是可用的。If the production is carried out in an open mould, it is preferably produced under an inert atmosphere. Oxygen is known to inhibit polymerization and lead to prolonged polymerization times. If a closed mold is used to form the polymer, the mold is advantageously composed of an inert material with low oxygen permeability and non-stick properties. Examples of suitable molding materials are polytetrafluoroethylenes such as Teflon® , silicone rubber, polyethylene, polypropylene and polyesters such as Mylar® . Glass molds and metal molds are also usable when using a release agent.
浇注静止模具，若使用具有内部曲线和外部曲线的模具，例如可以直接形成隐形眼镜。这样隐形眼镜可在一适宜的模具中通过聚合直接(“全塑模”方法)或只作好表面(“半塑模”方法)制造。Pouring static molds, for example contact lenses can be formed directly using molds with internal and external curves. Contact lenses can thus be manufactured in a suitable mold by polymerization directly ("full mold" method) or only the surface ("half mold" method).
按照本发明可同样使用旋转浇注(spin casting)，方法是，将一种本发明的原料溶液加到旋转铸件的模具中，使模具旋转，与此同时使溶剂蒸发。制好的隐形眼镜(其尺寸可通过模具尺寸，旋转速度和放入的溶液的粘度进行调控)留在模具中。Spin casting (spin casting) can also be used according to the invention, and the method is that a raw material solution according to the invention is added to the mold of the spin casting, and the mold is rotated, and the solvent is evaporated at the same time. The finished contact lens (the size of which can be adjusted by the size of the mold, the speed of rotation and the viscosity of the solution inserted) remains in the mold.
压制按照本发明例如是通过由本发明的聚合物薄膜的模压进行的。聚合物薄膜可以本身已知的方法例如通过浇注溶液制造。Pressing according to the invention is carried out, for example, by embossing from the polymer film according to the invention. The polymer film can be produced in a manner known per se, for example by casting the solution.
由例如前面已提到的制出的薄膜也可以本身已知的方法通过深冲或热成型制造隐形眼镜。Contact lenses can also be produced from films produced, for example, as already mentioned above, by deep drawing or thermoforming in a manner known per se.
同样旋转加工用作为制备本发明的隐形眼镜的最后方法步骤。若一例如按前面提到的方法得到的坯件还需进一步加工时，这种情况总是适用的。对旋转加工理解为这种本身已知的切削隐形眼镜-坯件的加工方法。相应的坯件例如可通过圆棒的挤压和其切开或由溶液浇注制造。与此有关切块(button)或半塑模产物，例如内部曲线坯件属于隐形眼镜-坯件概念。典型的坯件具有厚度为4或6mm和直径为10至17，例如12或14mm。对软物料可要求，在相应的加工前对物料冷冻，特别是在软化点以下，并必需时在加工期间维持为此要求的温度。Spinning is also used as the final process step in the preparation of the contact lenses of the present invention. This always applies if a blank obtained, for example, by the method mentioned above is to be processed further. Rotary machining is understood to mean this known machining method of cutting contact lens blanks. Corresponding blanks can be produced, for example, by extrusion and cutting of round rods or by solution casting. Buttons or semi-molded products in this connection, such as inner curve blanks, belong to the concept of contact lens blanks. Typical blanks have a thickness of 4 or 6 mm and a diameter of 10 to 17, eg 12 or 14 mm. For soft materials, it may be necessary to freeze the material prior to the corresponding processing, in particular below the softening point, and to maintain the temperature required for this during processing if necessary.
从坯件或按另外的一种方法制造的隐形眼镜出发，若后面还需对其表面附加精细加工时，按照本发明还可使用激光加工。Laser processing according to the invention can also be used if, starting from blanks or contact lenses produced by another method, additional fine processing of the surface is to be carried out later.
下面的实施例说明本发明的主题，但对它不限制在实施例的范围内。数量值的百分数只要不作其他说明是％重量。在下面的实施例中温度，若不作另外的说明的话，是以摄氏度公开的，分子量，也与一向在说明书中的一样，是平均分子量(标为：“Mw”)，若不作另外说明的话。The following examples illustrate the subject-matter of the invention without restricting it within the scope of the examples. Percentages of numerical values are % by weight unless stated otherwise. In the following examples temperatures are disclosed in degrees Celsius unless otherwise stated, and molecular weights, as always in the specification, are average molecular weights (designated: "Mw"), unless otherwise stated.
A-实施例：氮杂-光引发剂的制备A-Example: Preparation of aza-photoinitiators
实施例A1Example A1
2-二甲基氨基-2-苄基-1-(4-(2-羟基乙氧基)苯基)-丁烷-1-酮
标题化合物的制备依靠在EP-A-284,561所描述的合成步骤。The title compound was prepared by virtue of the synthetic procedure described in EP-A-284,561.
实施例A2Example A2
2-乙基-2-二甲基氨基-1-(4-(2-羟基乙氧基)苯基)-戊-4-烯-1-酮
实施例A3Example A3
1-(4-(2-羟基乙硫基)苯基)-2-甲基-2-吗啉代-丙烷-1-酮标题化合物的制备描述在EP-A-088,50中。1-(4-(2-Hydroxyethylthio)phenyl)-2-methyl-2-morpholino-propan-1-one The preparation of the title compound is described in EP-A-088,50.
实施例A4Example A4
1-(4-(2-羟基乙氧基)苯基)-2-甲基-吗啉代-丙烷-1-酮类似于实施例A3制备标题化合物。实施例A5下面化合物的制备：
实施例A6Example A6
类似于实施例A5由1.17g(4mmol)1(4-(2-羟基乙氧基)苯基)-2-甲基-2-吗啉代-丙烷-1-酮(来自实施例A4)，0.7g(4mmol)2，4-TDI用DBTDL作催化剂在二氯甲烷中制备下面的异氰酸酯。在向RG(反应混合物)中加入50ml醚和200ml石油醚后，标题化合物以结晶形式沉淀出来。将其过滤出来，用石油醚洗涤并接着在真空中干燥，得下述化合物，具有熔点为97-102℃：
并x∶y约是27∶1，并And x:y is about 27:1, and
n是5。n is 5.
在按实施例A5仪器中放入0.7g(1.3mmol)来自实施例A5的异氰酸酯，20ml干二氯甲烷和2.55g(0.51mVal NH2/g)氨基烷基聚硅氧烷KF 8003(Shin Etsu，日本)。此反应混合物在室温搅拌2小时和在40℃搅拌20分钟。此后在旋转蒸发器(RV)除去溶剂。残余物在真空中(40℃，0.001毫巴(0.1Pa))去掉剩余的溶剂。以定量的产率得到标题化合物。在红外光谱(IR)中不存在OCN-谱带。Into the apparatus according to Example A5 was placed 0.7 g (1.3 mmol) of the isocyanate from Example A5, 20 ml of dry methylene chloride and 2.55 g (0.51 mVal NH 2 /g) of aminoalkyl polysiloxane KF 8003 (Shin Etsu ,Japan). The reaction mixture was stirred at room temperature for 2 hours and at 40°C for 20 minutes. Thereafter the solvent was removed on a rotary evaporator (RV). The residue was freed of remaining solvent in vacuo (40°C, 0.001 mbar (0.1 Pa)). The title compound was obtained in quantitative yield. OCN-bands are absent in the infrared spectrum (IR).
实施例B2Example B2
类似于实施例B1由0.76g(1.3mmol)实施例A8的异氰酸酯和2.55g(0.51m Val NH2/g)氨基烷基聚硅氧烷KF8003(Shin Etsu，日本)出发，制备有实施例B1结构的低聚的光引发剂，其中R有下列含义： Analogously to Example B1, starting from 0.76 g (1.3 mmol) of the isocyanate of Example A8 and 2.55 g (0.51 m Val NH 2 /g) of aminoalkylpolysiloxane KF8003 (Shin Etsu, Japan), Example B1 was prepared The oligomeric photoinitiator of the structure, wherein R has the following meanings:
实施例B3Example B3
类似于实施例B1由0.55g(0.97mmol)异氰酸酯(来自实施例A8)和1.47g(0.7mVal NH2/g)氨基烷基聚硅氧烷X-22-161B(Shin Etsu，日本)出发制备一种具有下面结构的低聚的光引发剂：其中x约是38，和R相当于减去了异氰酸酯的来自实施例A8标题化合物的基。Prepared analogously to Example B1 starting from 0.55 g (0.97 mmol) of isocyanate (from Example A8) and 1.47 g (0.7 mVal NH 2 /g) of aminoalkylpolysiloxane X-22-161B (Shin Etsu, Japan) An oligomeric photoinitiator having the following structure: wherein x is about 38, and R corresponds to the radical from the title compound of Example A8 minus the isocyanate.
实施例B4Example B4
类似于实施例B1使1.0g(1.95mmol)来自实施例A5的异氰酸酯在20ml干的乙腈中的溶液与2.24g(0.84mVal NH2/g)杰弗胺(Jeffamine ED)2001(Texaco，USA)在30ml干乙腈中混合并在室温搅拌24小时。在加工后得3.2g(99％)下面的光引发剂：R-NHCONH-CHCH3CH2-(OCHCH3CH2)a-(OCH2CH2)b-(OCHCH3CH2)c-NHCONH-R其中a+c＝2.5和b＝40.5，并R相当于减去了异氰酸酯的来自实施例A5标题化合物的基。Similar to Example B1, a solution of 1.0 g (1.95 mmol) of the isocyanate from Example A5 in 20 ml of dry acetonitrile was mixed with 2.24 g (0.84 mVal NH 2 /g) of Jeffamine ED 2001 (Texaco, USA) Mix in 30 ml of dry acetonitrile and stir at room temperature for 24 hours. 3.2 g (99%) of the following photoinitiator were obtained after processing: R -NHCONH-CHCH3CH2-( OCHCH3CH2 ) a- ( OCH2CH2 ) b- ( OCHCH3CH2 ) c -NHCONH -R where a+c=2.5 and b=40.5, and R corresponds to the radical from the title compound of Example A5 minus the isocyanate.
实施例B5Example B5
在按实施例A5仪器中在氮气下在80℃使1.65g聚乙烯醇(PVA)(Serva03/20，分子量约13000)溶入干的NMP。然后冷却至室温并掺入1.0g(1.88mmol)来自实施例A7的异氰酸酯在10ml干NMP中的溶液和5mg DBTDL作为催化剂，然后将此混合物加温至40℃48小时。在此时间以后用红外线证明在2250cm-1无OCN出现。冷却反应混合物(RG)至室温并掺入700ml二乙醚，与此同时沉淀出产物。过滤，用乙醚洗涤并接着在真空中干燥。余下1.9g白色产物，按照元素分析该产物含有2.20％S。质子核磁共振(NMR)测定与下述结构一致：1.65 g of polyvinyl alcohol (PVA) (Serva® 03/20, molecular weight ca. 13000) were dissolved in dry NMP in an apparatus according to Example A5 at 80° C. under nitrogen. It is then cooled to room temperature and a solution of 1.0 g (1.88 mmol) of the isocyanate from example A7 in 10 ml of dry NMP and 5 mg of DBTDL are added as catalyst and the mixture is then warmed to 40° C. for 48 hours. After this time no OCN appeared at 2250 cm -1 as evidenced by infrared rays. The reaction mixture (RG) was cooled to room temperature and 700 ml diethyl ether was added, at which time the product precipitated. Filtered, washed with ether and then dried in vacuo. 1.9 g of white product remained, which contained 2.20% S by elemental analysis. Proton nuclear magnetic resonance (NMR) measurements were consistent with the following structure:
-[(CH2-CHOH)a-(CH2-CHOCONHR)b]n--[(CH 2 -CHOH) a -(CH 2 -CHOCONHR) b ] n -
其中n约是10和a∶b＝20∶1；和R相当于减去了异氰酸酯的来自实施例7标题化合物的基。wherein n is about 10 and a:b=20:1; and R corresponds to the radical from the title compound of Example 7 minus the isocyanate.
实施例B6，B7和B8Examples B6, B7 and B8
类似于实施例B5使二种羟烷基取代的聚二甲基硅氧烷(KF-6002/KF-6001)和一葡聚糖与来自实施例A7的异氰酸酯反应。下面的参数描述了这种化合物，对所有化合物产率约为90％。这种化合物的硫含量利用燃烧分析测定(表的末列)。实施例A7的 OH-大基体 溶剂 S-含量(％)异氰酸酯 理论值/测定值0.5g KF-6002，Shin-Etsu，JP THF(0.94mmol) 1.5g(0.63 Val OH/g) 1.50/1.380.5g KF-6001，Shin-Etsu，JP(0.94mmol) 0.85g(1.1m Val OH/g) THF 2.22/2.080.5g Dextran 8，Serva G(0.94mmol) 2.3g，MG＝8-12000 DMSO 1.08/0.99Two hydroxyalkyl-substituted polydimethylsiloxanes (KF-6002/KF-6001 ) and monodextran were reacted with the isocyanate from Example A7 analogously to Example B5. The parameters below describe this compound and yields were approximately 90% for all compounds. The sulfur content of this compound was determined using combustion analysis (last column of the table). Example A7's OH-large-substrate solvent S-content ( %) theoretical value/determination value of isocyanate 0.5g KF-6002, SHIN-ETSU, JP THF (0.94mmol) 1.5g (0.63 value) 1.50/1.380. 5G KF-6001, SHIN-ETSU, JP (0.94mmol) 0.85g (1.1M Val OH/G) THF 2.22/2.080.5G Dextran 8, SERVA G (0.94mmol) 2.3g, MG = 8-12000 DMSO 1.08/ 0.99
实施例B9Example B9
类似于实施例B5在12小时内使3.23g胶原(Serva 1744，MG≈80000)溶入二甲基亚砜中(DMSO)并接着掺入1.0g(1.9mmol)来自实施例A8的异氰酸酯在10ml二甲基亚砜中。在室温搅拌72小时后用500ml甲醇稀释反应混合物，接着沉淀出产物。将其过滤分离并多次用干四氢呋喃洗涤。然后在高真空中干燥(0.1Pa，室温，72小时)。余下2.8g黄-白色产物，其红外光谱和质子核磁共振与期待的结构相一致。3.23 g of collagen (Serva 1744, MG≈80000) were dissolved in dimethylsulfoxide (DMSO) analogously to Example B5 within 12 hours and then 1.0 g (1.9 mmol) of isocyanate from Example A8 were incorporated in 10 ml in dimethylsulfoxide. After stirring at room temperature for 72 hours the reaction mixture was diluted with 500 ml of methanol and the product precipitated out. It was isolated by filtration and washed several times with dry THF. It was then dried in high vacuum (0.1 Pa, room temperature, 72 hours). 2.8 g of yellow-white product remained, whose IR spectrum and proton NMR were consistent with the expected structure.
实施例B10Example B10
全氟聚醚大基体的制备(Fomblin ZDOL TX1000)，两侧末端带有一含异佛尔酮二异氰酸酯的光引发剂Preparation of perfluoropolyether macromatrix (Fomblin ZDOL TX1000) with a photoinitiator containing isophorone diisocyanate at both ends
在一带有回流冷却器，温度计，搅拌器和氮气导入管的100ml圆烧瓶中使4.46g(0.01mol)活性的光引发剂(按EP-A-632,329的实施例A1制备)溶10g干的四氢呋喃中并与5.73g(0.005mol)Fomblin ZDOL TX1000，分子量＝1146(Ausimont SpA，Milano，意大利)混合。对此加入2mg催化剂DBTDL并在40℃搅拌72小时。在此反应时间后红外光谱分光仪可证明不再有未反应的异氰酸酯。在冷却至室温后在旋转蒸发器通过蒸发除去溶剂。得到一种高粘度的，无色的油，再在高真空中脱除痕量的溶剂。产物的结构利用1H-NMR-光谱证实。In a 100ml round flask with reflux cooler, thermometer, stirrer and nitrogen inlet tube, make 4.46g (0.01mol) active photoinitiator (prepared by the embodiment A1 of EP-A-632,329) dissolve 10g dry tetrahydrofuran Neutralized and mixed with 5.73 g (0.005 mol) of Fomblin ZDOL TX1000, molecular weight = 1146 (Ausimont SpA, Milano, Italy). To this, 2 mg of the catalyst DBTDL are added and stirred at 40° C. for 72 hours. After this reaction time infrared spectrometry can demonstrate that there is no more unreacted isocyanate. After cooling to room temperature the solvent was removed by evaporation on a rotary evaporator. A highly viscous, colorless oil was obtained and traces of solvent were removed in high vacuum. The structure of the product was confirmed by means of 1 H-NMR-spectroscopy.
C-实施例：线性的三嵌段-大基体的制备C-Example: Preparation of linear triblock-macromatrix
实施例C1：Example C1:
在一带有回流冷却器，搅拌器和氩导入管的褐色圆烧瓶中使800mg(0.2mmol)大光引发剂(来自按EP-A-632,329的实施例B6)在氩气下溶入4ml干的四氢呋喃中。对此加入2.95g(20mmol)新蒸馏的甲基丙烯酸2-羟丙基酯(2-HPMA)并搅拌60分钟。圆烧瓶与其内容物接着浸入液氮中10分钟并使冷冻的溶液在负压下(0.004mbar)脱气15分钟。用氩去除真空并加温溶液至室温并通入氩15分钟。在通过0.45μm孔眼的过滤器过滤后干净的聚丙烯-模具在氮气下灌入这种溶液(每模约200μl溶液)，封闭并用紫外光辐射20分钟(12mW/cm2)。带有高粘度的聚合物溶液的模具接着在40℃的烘箱中除去四氢呋喃。余下清澈透明的小片(Disks)，它们是可溶入乙醇的。按GPC分析的三嵌段-大基体的Mw是18700。其中应注意的是：GPC只表明了三嵌段共聚物的形成并没有观察到作为副产物的所用乙烯基单体的均聚物。In a brown round flask with reflux cooler, stirrer and argon inlet tube, 800 mg (0.2 mmol) of macrophotoinitiator (from Example B6 according to EP-A-632,329) was dissolved under argon in 4 ml of dry in tetrahydrofuran. To this, 2.95 g (20 mmol) of freshly distilled 2-hydroxypropyl methacrylate (2-HPMA) were added and stirred for 60 minutes. The round flask with its contents was then immersed in liquid nitrogen for 10 minutes and the frozen solution was degassed under negative pressure (0.004 mbar) for 15 minutes. The vacuum was removed with argon and the solution was warmed to room temperature with argon sparging for 15 minutes. Clean polypropylene molds after filtration through a 0.45 μm filter are filled with this solution under nitrogen (ca. 200 μl solution per mold), closed and irradiated with UV light for 20 minutes (12 mW/cm 2 ). The mold with the highly viscous polymer solution was then removed from the tetrahydrofuran in a 40°C oven. Clear and transparent disks (Disks) remained, which were soluble in ethanol. The Mw of the triblock-macromatrix was 18700 by GPC. It should be noted here that GPC only indicated the formation of triblock copolymers and no homopolymers of the vinyl monomers used were observed as by-products.
实施例C2：Example C2:
类似于实施例C1使1.96g(0.5mmol)硅氧烷-大光引发剂B6(按EP-A-632329)溶入4ml干四氢呋喃中(在惰性气氛下)。对此加入720mg(5mmol)新蒸馏的甲基丙烯酸2-羟丙基酯并搅拌60分钟。下面的试样制剂与在实施例C1中的相同。这种三嵌段-大基体的Mw按照GPC-分析相当于7800。其中注意的是，GPC只表明三嵌段-共聚物的形成并与此同时没有观察到作为副产物的所用乙烯基单体的均聚物。Analogously to example C1, 1.96 g (0.5 mmol) of siloxane-large photoinitiator B6 (according to EP-A-632329) were dissolved in 4 ml of dry tetrahydrofuran (under inert atmosphere). To this were added 720 mg (5 mmol) of freshly distilled 2-hydroxypropyl methacrylate and stirred for 60 minutes. The following sample formulations were the same as in Example C1. The Mw of this triblock-macromatrix corresponds to 7800 according to GPC-analysis. It is noted here that GPC only shows the formation of triblock copolymers and at the same time no homopolymers of the vinyl monomers used are observed as by-products.
实施例C3至C9：Examples C3 to C9:
相应于实施例C1制备了另外的具有不同的大光引发剂(参见B-实施例)的以及具有共聚用单体不同类别和组成的三嵌段-大基体。下面的表格中含有最重要的参数(缩写具有下面的含义：HEMA＝甲基丙烯酸2-羟乙基酯，2-HPMA＝甲基丙烯酸2-羟基丙基酯，PME 400＝聚乙二醇(分子量400)甲基丙烯酸酯，NVP＝N-乙烯基-2-吡咯烷酮)：Further triblock-macromatrixes with different macrophotoinitiators (see B-example) and with different classes and compositions of comonomers were prepared corresponding to Example C1. The most important parameters are contained in the table below (abbreviations have the following meanings: HEMA = 2-hydroxyethyl methacrylate, 2-HPMA = 2-hydroxypropyl methacrylate, PME 400 = polyethylene glycol ( Molecular weight 400) methacrylate, NVP=N-vinyl-2-pyrrolidone):
实施例C3：Example C3:
大引发剂(“MI”)： 按EP-A-632329的B10Macroinitiator ("MI"): B10 per EP-A-632329
共聚用单体： HEMA，Comonomer: HEMA,
MI/共聚用单体比(mol/mol) 1∶13，MI/comonomer ratio (mol/mol) 1:13,
溶剂，浓度： 乙醇，33％Solvent, Concentration: Ethanol, 33%
辐射时间(分钟)： 20，Radiation time (minutes): 20,
按GPC产物的Mw： 3547。Mw by GPC product: 3547.
实施例C4：Example C4:
大引发剂(“MI”) 按EP-A-632329的B10Macroinitiator ("MI") as per B10 of EP-A-632329
共聚用单体： PME 400，Comonomer: PME 400,
MI/共聚用单体比(mol/mol) 1∶100，MI/comonomer ratio (mol/mol) 1:100,
溶剂，浓度： THF，50％Solvent, concentration: THF, 50%
辐射时间(分钟)： 25，Radiation time (minutes): 25,
按GPC产物的Mw： 39620。Mw according to GPC product: 39620.
实施例C5Example C5
大引发剂(“MI”)： 按EP-A-632329的B6Macroinitiator ("MI"): as per B6 of EP-A-632329
共聚用单体： HEMA，Comonomer: HEMA,
MI/共聚用单体比(mol/mol) 1∶10，MI/comonomer ratio (mol/mol) 1:10,
溶剂，浓度： THF，50％Solvent, concentration: THF, 50%
辐射时间(分钟)： 25，Radiation time (minutes): 25,
按GPC产物的Mw： 13590。Mw by GPC product: 13590.
实施例C6Example C6
大引发剂(“MI”) 按EP-A-632329的B2Macroinitiator ("MI") as per B2 of EP-A-632329
共聚用单体： 2-HPMA，Comonomer: 2-HPMA,
MI/共聚用单体比(mol/mol) 1∶35，MI/comonomer ratio (mol/mol) 1:35,
溶剂，浓度： THF，35％，Solvent, concentration: THF, 35%,
辐射时间(分钟)： 20，Radiation time (minutes): 20,
按GPC产物的Mw： 26600。Mw by GPC product: 26600.
实施例C7：Example C7:
大光引发剂(“MI”) 按EP-A-632329的B2Large photoinitiator ("MI") as per B2 of EP-A-632329
共聚用单体： PME 400，Comonomer: PME 400,
MI/共聚用单体比(mol/mol) 1∶100，MI/comonomer ratio (mol/mol) 1:100,
溶剂，浓度： THF，50％，Solvent, concentration: THF, 50%,
辐射时间(分钟)： 25，Radiation time (minutes): 25,
按GPC产物的Mw： 97651。Mw by GPC product: 97651.
实施例C8：Example C8:
大引发剂(“MI”) B10Macroinitiator ("MI") B10
共聚用单体： 2-HPMA，Comonomer: 2-HPMA,
MI/共聚用单体比(mol/mol) 1∶6，MI/comonomer ratio (mol/mol) 1:6,
溶剂，浓度： THF，30％，Solvent, concentration: THF, 30%,
辐射时间(分钟)： 20，Radiation time (minutes): 20,
按GPC产物的Mw： 1900。Mw by GPC product: 1900.
实施例C9：Example C9:
大引发剂(“MI”) B4Macroinitiator ("MI") B4
共聚用单体： NVP，Comonomer: NVP,
MI/共聚用单体比(mol/mol) 1∶10，MI/comonomer ratio (mol/mol) 1:10,
溶剂，浓度： 乙醇，30％Solvent, Concentration: Ethanol, 30%
辐射时间(分钟)： 20，Radiation time (minutes): 20,
按GPC产物的Mw： 2960。Mw by GPC product: 2960.
实施例C10：Example C10:
来自实施例B3的2.0g大引发剂在氮气下溶入3ml干THF中。在2g这种溶液中混入0.9g(8mmol)新蒸馏的NVP并通氮气30分钟。然后在氮气下用这种溶液装满干净的聚丙烯模具(每模约200μl溶液)，封闭并用紫外光(12.5mW/cm2)辐射10分钟。具有高粘度的聚合物溶液的模具接着在40℃的烘箱中去掉THF。余下清澈的，浅黄的片(Disk)，它们在乙醇中是可溶解的。按GPC的Mw为约5800。2.0 g of macroinitiator from Example B3 were dissolved in 3 ml of dry THF under nitrogen. To 2 g of this solution was mixed 0.9 g (8 mmol) of freshly distilled NVP and purged with nitrogen for 30 minutes. Clean polypropylene molds (about 200 μl solution per mold) were then filled with this solution under nitrogen, sealed and irradiated with UV light (12.5 mW/cm 2 ) for 10 minutes. The mold with high viscosity polymer solution was then removed from THF in an oven at 40°C. Clear, pale yellow disks (Disks) remained, which were soluble in ethanol. Mw by GPC is about 5800.
实施例C11：Example C11:
类似于实施例C10由2.0g来自实施例B3的大引发剂和0.9g(8.15mmol)二甲基丙烯酰胺(DMA)的混合物制备透明的，稍模糊的盘片。这种三嵌段-大基体的Mw按GPC相当于5560。A clear, slightly hazy disc was prepared analogously to Example C10 from a mixture of 2.0 g of the macroinitiator from Example B3 and 0.9 g (8.15 mmol) of dimethylacrylamide (DMA). The Mw of this triblock-macromatrix corresponds to 5560 by GPC.
D-实施例：交联盘片或镜片的制造D-Example: Fabrication of Crosslinked Discs or Lenses
实施例D1：Example D1:
使按EP-A-632329的B6的2.0g(0.5mmol)大光引发剂在一20ml圆烧瓶中在氮气氛下溶入3ml乙醇中。在加入2.6g(0.02mol)HEMA和0.4g(8％)乙二醇二(甲基丙烯酸)酯(EGDMA)作交联剂后在氮气下在2小时内搅拌反应混合物。然后用液氮冰冻溶液并在高真空中(0.004毫巴)脱气15分钟。下面的样品制备以及聚合是在手套箱(Glove Box)里面在隔绝氧的情况下进行的。先搅拌反应混合物15分钟，然后微过滤(0.45m过滤器)并接着装入丙烯模具。不仅可以使用隐形眼镜模具也可使用圆形的小片模具(Disk)。封闭的模具在一为此安装的紫外-炉中在紫外光强度为12.5mW/cm2时辐射20分钟。制成的盘片或镜片在乙醇中提取24小时并在高真空中在40℃和10-3托干燥。盘片表明E-模量为2.1MPa和透氧性为98Barrer。2.0 g (0.5 mmol) of macrophotoinitiator according to B6 of EP-A-632329 were dissolved in 3 ml of ethanol in a 20 ml round flask under nitrogen atmosphere. After addition of 2.6 g (0.02 mol) HEMA and 0.4 g (8%) ethylene glycol di(methacrylate) (EGDMA) as crosslinker, the reaction mixture was stirred under nitrogen within 2 hours. The solution was then frozen with liquid nitrogen and degassed in high vacuum (0.004 mbar) for 15 min. The following sample preparation and polymerization were carried out in a glove box (Glove Box) under the exclusion of oxygen. The reaction mixture was first stirred for 15 minutes, then microfiltered (0.45m filter) and then filled into propylene molds. Not only contact lens molds but also circular disk molds can be used. The closed mold was irradiated for 20 minutes at a UV intensity of 12.5 mW/cm 2 in a UV furnace fitted for this purpose. The finished disks or lenses were extracted in ethanol for 24 hours and dried in high vacuum at 40°C and 10 -3 Torr. The disk showed an E-modulus of 2.1 MPa and an oxygen permeability of 98 Barrer.
实施例D2：Example D2:
类似于实施例D1由按EP-A-632329的实施例B6的2.0g(0.5mmol)大引发剂，1.3g(10mmol)HEMA，0.23g(6.5％)EGDMA和3ml异丙醇制备镜片和盘片。Lenses and discs were prepared analogously to Example D1 from 2.0 g (0.5 mmol) macroinitiator according to Example B6 of EP-A-632329, 1.3 g (10 mmol) HEMA, 0.23 g (6.5%) EGDMA and 3 ml isopropanol piece.
实施例D3：Example D3:
类似于实施例D1由按EP-A-632329的实施例B6的1g(0.25mmol)大引发剂，1g(10mmol)DMA，0.2g(9％)EGDMA和2.2g异丙醇制备镜片。A lens was prepared analogously to Example D1 from 1 g (0.25 mmol) macroinitiator according to Example B6 of EP-A-632329, 1 g (10 mmol) DMA, 0.2 g (9%) EGDMA and 2.2 g isopropanol.
实施例D4：Example D4:
类似于实施例D1由实施例B1的3.45g大引发剂，5.95g甲基丙烯酸3-〔三(三甲基甲硅烷氧基)-甲硅烷基〕丙基酯(TRIS)，0.6g NVP和0.5g(4.75％)EGDMA制备镜片，其中TRIS和NVP用作相应的大引发剂的溶剂。Similar to Example D1 by the 3.45g large initiator of embodiment B1, 5.95g 3-[tris(trimethylsilyloxy)-silyl]propyl methacrylate (TRIS), 0.6g NVP and Lenses were prepared with 0.5 g (4.75%) EGDMA in which TRIS and NVP were used as solvents for the corresponding macroinitiators.
实施例D5：Example D5:
类似于实施例D1由实施例B3的3.92g(1mmol)大引发剂，3.92g(8mmol)PME 400，和0.5g(6％)EGDMA制备盘片。使用THF(5ml)作为溶剂。Discs were prepared analogously to Example D1 from 3.92 g (1 mmol) macroinitiator of Example B3, 3.92 g (8 mmol) PME 400, and 0.5 g (6%) EGDMA. THF (5 ml) was used as solvent.
实施例D6：Example D6:
类似于实施例D1由实施例B10的1.0g(0.5mmol)大引发剂，0.28g(2.5mmol)NVP，0.1g(7.2％)EGDMA和1g THF制备盘片。Discs were prepared analogously to Example D1 from 1.0 g (0.5 mmol) macroinitiator, 0.28 g (2.5 mmol) NVP, 0.1 g (7.2%) EGDMA and 1 g THF from Example B10.
下面的概况表明得到的镜片和盘片的性能：实施例 吸水性 E-模量 断裂伸长The following profiles demonstrate the properties of the resulting lenses and discs: Examples Water Absorption E-Modulus Elongation at Break
(％) (MPa) (％)(%) (MPa) (%)
D2 25，2 2，8 140D2 25, 2 2, 8 140
D3 39，1 3，6 69D3 39, 1 3, 6 69
D4 5，2 0，1 97.4D4 5, 2 0, 1 97.4
D5 41，1 0，8 144D5 41, 1 0, 8 144
D6 4，0 3，0 74D6 4,0 3,0 74
实施例D7：Example D7:
按EP-A-632329实施例B5的2.5g(0.3mmol)大引发剂在氮气下溶入4ml干乙醇中。对此加入新蒸馏的2.4g(0.018mol)HEMA和4.0g(7.5％)交联剂EGDMA。然后在氮气下搅拌30分钟并接着通氮气15分钟。然后将溶液过滤入一瓶中(孔眼0.45μm)。在氮气下使溶液装入干净的聚丙烯-模具中(每模200μl)，封闭模具并用紫外光辐射25分钟。打开模具并将含镜片的一半模具放入乙醇浴中，与此同时镜片从半模松开。然后镜片在乙醇中再提取24小时并接着在高真空(10-4托)中干燥。在压煮后对镜片进行分析。镜片显示透氧性为91.3Barrer和接触角为110°(前进角)和102°(后退角)。2.5 g (0.3 mmol) of macroinitiator according to example B5 of EP-A-632329 were dissolved in 4 ml of dry ethanol under nitrogen. To this were added 2.4 g (0.018 mol) of freshly distilled HEMA and 4.0 g (7.5%) of the crosslinker EGDMA. It was then stirred under nitrogen for 30 minutes followed by nitrogen sparging for 15 minutes. The solution was then filtered into a vial (pore size 0.45 μm). The solution was filled under nitrogen into clean polypropylene-molds (200 μl per mold), the molds were closed and irradiated with UV light for 25 minutes. The mold was opened and the mold half containing the lens was placed in an ethanol bath while the lens was released from the mold half. The lenses were then extracted in ethanol for an additional 24 hours and then dried in high vacuum (10 −4 Torr). Lenses were analyzed after autoclaving. The lenses exhibited an oxygen permeability of 91.3 Barrer and contact angles of 110° (advancing angle) and 102° (receding angle).
实施例D8Example D8
来自实施例B5的0.16g大光引发剂在氮气下溶入N-甲基吡咯烷酮(NMP)在DMSO(70∶12)中的0.82g溶液中。对此加入20μg交联剂EGDMA并接着通入氮气20分钟。然后将溶液滤入瓶中(四氟乙烯过滤器，孔眼0.45μm)。在氮气下用这种溶液装入干净的聚丙烯-模具(每模180-200μl)，封闭模具并用紫外光辐射30分钟(12mW/cm2)。打开模具并将含镜片的一半模放入乙醇浴中，与此同时透明的，弱黄色的镜片从半模上松下来。然后将镜片在乙醇中再提取24小时并接着在真空干燥。0.16 g of the macrophotoinitiator from Example B5 was dissolved under nitrogen in 0.82 g of a solution of N-methylpyrrolidone (NMP) in DMSO (70:12). To this, 20 μg of the crosslinker EGDMA are added and nitrogen is then purged for 20 minutes. The solution was then filtered into a bottle (tetrafluoroethylene filter, pores 0.45 μm). Clean polypropylene-molds (180-200 μl per mold) are filled with this solution under nitrogen, the molds are closed and irradiated with UV light for 30 minutes (12 mW/cm 2 ). The mold was opened and the mold half containing the lens was placed in an ethanol bath while the clear, slightly yellow lens was loosened from the mold half. The lenses were then extracted in ethanol for an additional 24 hours and then dried in vacuo.
实施例D9Example D9
类似于实施例D8由来自实施例B5的0.1g大光引发剂，0.5gDMSO，0.4gNVP和20μg EGDMA制备隐形眼镜。Contact lenses were prepared analogously to Example D8 from 0.1 g macrophotoinitiator, 0.5 g DMSO, 0.4 g NVP and 20 μg EGDMA from Example B5.
实施例D10Example D10
来自实施例B8的0.25g大光引发剂在氮气下溶入0.5g干的DMSO中。对此加入0.25g HEMA和20μg交联剂EGDMA。接着通入氮气30分钟。然后过滤溶液(孔眼0.45μm)并在氮气下装入干净聚丙烯-模具中。如在实施例D8中辐射并加工。0.25 g of the macrophotoinitiator from Example B8 was dissolved in 0.5 g of dry DMSO under nitrogen. To this was added 0.25 g HEMA and 20 μg cross-linker EGDMA. Nitrogen was then bubbled in for 30 minutes. The solution was then filtered (pore size 0.45 μm) and filled into clean polypropylene molds under nitrogen. Irradiated and processed as in Example D8.
下表给出这样制备的隐形眼镜的参数(其中“应变”也称“断裂伸长”)：实施例 吸水性 应变 E-模量The following table gives the parameters of the contact lenses thus prepared (where "strain" is also called "elongation at break"): Example Water absorption Strain E-modulus
(％) (％) (MPa)D8 178 490 0.04D9 441 73 0.24D10 19 67 0.52( %) ( %) (Mpa) D8 178 490 0.04D9 441 73 0.24D10 19 67 0.52
实施例D11：Example D11:
类似于实施例D8用下述的组合物进行聚合：实施例B4的大引发剂(20％)，DMA(20％)，TRIS(5％)，EGDMA(5％)。替代NMP和DMSO聚合在乙醇(40％)中进行。镜片表明吸水性为160％和E-模量为0.34MPa。Polymerization was carried out analogously to Example D8 with the following composition: macroinitiator from Example B4 (20%), DMA (20%), TRIS (5%), EGDMA (5%). Instead of NMP and DMSO polymerizations were carried out in ethanol (40%). The lenses showed a water absorption of 160% and an E-modulus of 0.34 MPa.
实施例D12：Example D12:
2.5g在实施例C5中描述的三嵌段共聚物(由中央的聚硅氧烷嵌段和二个末端的聚-HEMA-嵌段构成)在干氮气下溶入3.5ml干THF中并掺0.08g甲基丙烯酸2-异氰酸根合乙基酯(IEM)以及5mg二月桂酸二丁基锡。此混合物在40℃2搅拌24小时，直至所有的IEM都已反应(红外光谱)。然后通过加入0.25gDMA以及150mg Irgacure 184作为光引发剂配制隐形眼镜配方。按照实施例D1用这种配方制造软的隐形眼镜。在压煮以后这样得到的隐形眼镜表明透氧性为87 barrer。2.5 g of the triblock copolymer described in Example C5 (consisting of a central polysiloxane block and two terminal poly-HEMA-blocks) was dissolved in 3.5 ml of dry THF under dry nitrogen and mixed with 0.08 g of 2-isocyanatoethyl methacrylate (IEM) and 5 mg of dibutyltin dilaurate. This mixture was stirred at 40°C2 for 24 hours until all the IEM had reacted (IR spectrum). Contact lens formulations were then formulated by adding 0.25 g DMA and 150 mg Irgacure 184 as photoinitiators. Soft contact lenses were made from this formulation according to Example D1. The contact lenses thus obtained showed an oxygen permeability of 87 barrer after autoclaving.